CN111448220A - Polysaccharide derivatives - Google Patents

Abstract

The present invention relates to a polysaccharide derivative which can improve the cleaning performance of clothes and the like and can inhibit the recontamination caused by powder dirt during cleaning. The present invention relates to a polysaccharide derivative having a cationic group and a hydrocarbon group (R) having 2 or more carbon atoms, wherein the hydrocarbon group (R) is bonded directly or through a hydrocarbon group having an oxygen atom to a group obtained by removing a hydrogen atom from a hydroxyl group of a hydroxyalkylated polysaccharide, wherein the hydroxyalkylated polysaccharide is a hydroxyethylated polysaccharide or a hydroxypropylated polysaccharide, and the hydroxyalkylated polysaccharide has a weight average molecular weight of 1 to 74 million.

Description

Polysaccharide derivatives

Technical Field

The present invention relates to a polysaccharide derivative.

Prior Art

Polysaccharide derivatives are used as formulation components for detergent compositions and the like, and have a wide range of applications.

For example, jp 2000 a-178303 (patent document 1) describes a polysaccharide derivative in which some or all of the hydrogen atoms of the hydroxyl groups of a polysaccharide or a derivative thereof are substituted with the following groups (a), (B) and (C) as an agent useful as a softening agent for laundry.

(A) A C10-43 linear or branched alkyl, alkenyl or acyl group which may be substituted with a hydroxyl group or may be inserted with an oxycarbonyl group (-COO-or-OCO-) or an ether bond

(B) Carboxymethyl or a salt thereof

(C) Specific cationic groups

Jp 2015-168666 a (patent document 2) discloses an aqueous hair cleansing agent that has excellent smoothness of hair during cleansing and rinsing even when the hair is damaged and can impart a moist feel to dried hair, wherein the aqueous hair cleansing agent contains the following components (a), (B), and (C) and water, and has a pH value of 2 to 6 at 25 ℃ when diluted to 20 times by mass with water.

(A) Anionic surfactants

(B) Having a main chain derived from anhydroglucose, wherein the degree of substitution of cationic oxyalkylene groups per anhydroglucose unit is 0.01 to 1.0, the degree of substitution of glyceryl groups is 0.5 to 5.0, and the degree of substitution of groups containing hydrocarbon groups having 3 to 18 carbon atoms is 0 to 0.2

(C) Monoalkyl or monoalkenyl glyceryl ether having C4-12 alkyl or alkenyl group

In japanese patent publication No. 2013-529644 (patent document 3), there is disclosed a personal care composition additive for imparting a lasting effect on a keratinous surface, comprising: a) a persistent polymer and b) a water-miscible polar solvent, wherein the concentration of the persistent polymer and the water-miscible polar solvent relative to the solvent of the solution is in the range of about 0.1 to about 20 mass%, the molecular weight (Mw) of the persistent polymer determined by size exclusion chromatography is in the range of more than about 50kDa and not more than about 800kDa, the cationic substitution degree of the persistent polymer is more than about 0.001 unit, and the persistent polymer is selected from polysaccharides and synthetic polymers containing cationic monomers.

U.S. patent application publication No. 2013/0130949 (patent document 4) discloses a viscosity modifier for drilling agents and the like, which uses a high molecular weight cellulose having a hydrophobic substituent and a cationic or anionic substituent and having high thermal stability.

Disclosure of Invention

The invention relates to the following <1> and <2 >.

<1> a polysaccharide derivative which has a cationic group and a hydrocarbon group (R) having 2 or more carbon atoms, wherein the hydrocarbon group (R) is bonded directly or through a hydrocarbon group having an oxygen atom to a group obtained by removing a hydrogen atom from a hydroxyl group of a hydroxyalkylated polysaccharide, wherein the hydroxyalkylated polysaccharide is a hydroxyethylated polysaccharide or a hydroxypropylated polysaccharide, and wherein the hydroxyalkylated polysaccharide has a weight average molecular weight of 1 to 74 million.

< 2> A process for producing a polysaccharide derivative, which comprises introducing a hydrocarbon group (R) having 2 or more carbon atoms into a hydroxyalkylated polysaccharide having a weight average molecular weight of 1 to 74 million, and then reacting the resultant with a cationizing agent, as described in <1 >.

Detailed Description

As a cleaning component for clothes, a cleaning component is required which can suppress the firm adhesion of sebum dirt, improve the cleaning property of sebum dirt at the time of cleaning, and suppress the recontamination of powder dirt such as carbon.

However, the conventional agents cannot exert sufficient performance.

The present invention relates to a polysaccharide derivative which can improve the cleaning performance of sebum dirt during cleaning and can inhibit the recontamination caused by powder dirt during cleaning.

The present inventors found that: the above problems are solved by specific polysaccharide derivatives.

The present invention provides a polysaccharide derivative which can improve the cleaning performance of sebum dirt during cleaning and can suppress recontamination due to powder dirt during cleaning.

In the following description, the term "cleaning performance" means a performance of suppressing firm adhesion of sebum dirt during use such as wearing and improving a performance of removing sebum dirt during cleaning, and the term "anti-redeposition performance" means a performance of suppressing redeposition due to powdery dirt during cleaning.

[ polysaccharide derivatives ]

The polysaccharide derivative of the present invention has a cationic group and a hydrocarbon group (R) having 2 or more carbon atoms (hereinafter, also simply referred to as "hydrocarbon group (R)"), and the hydrocarbon group (R) is bonded directly or through a hydrocarbon group having an oxygen atom to a group obtained by removing a hydrogen atom from a hydroxyl group of a hydroxyalkylated polysaccharide, and the hydroxyalkylated polysaccharide is a hydroxyethylated polysaccharide or a hydroxypropylated polysaccharide, and has a weight average molecular weight of 1 to 74 million.

The present inventors found that: when a detergent composition or the like containing the polysaccharide derivative of the present invention is used for treating a fabric such as clothes, adhesion of sebum dirt is suppressed, and recontamination due to powder dirt during washing is suppressed. The detailed mechanism of action is not clear, but some of them are presumed as follows.

When the polysaccharide derivative of the present invention has a cationic group, the polysaccharide derivative is adsorbed on the surface of a fabric by electrostatic interaction with an anionic surfactant adsorbed on the surface of the fabric when clothes and the like are treated by electrostatic interaction with an anionic group of a hydrophobic fiber or in the presence of an anionic surfactant. Further, the polysaccharide derivative of the present invention has a hydrocarbon group (R) having 2 or more carbon atoms, and particularly when the fabric is hydrophobic, the polysaccharide derivative is adsorbed on the surface of the fabric by hydrophobic interaction. In this way, by having a cationic group and a hydrocarbon group (R), the adsorption to the fabric is improved.

It is considered that adsorption of the polysaccharide derivative of the present invention on the surface of a fabric makes the surface of the fabric made of hydrophobic fibers hydrophilic and improves oil repellency. It is thus presumed that firm adhesion of sebum dirt is suppressed.

The reason why the weight average molecular weight of the polysaccharide derivative of the present invention is less than a specific amount and the re-contamination of powder dirt is also suppressed is presumed to be: since the polysaccharide derivative of the present invention is more uniformly adsorbed on the fiber surface, the cationic group of the polysaccharide derivative is delocalized, and the cationic group is likely to cause an electrostatic interaction with the anionic group of the fiber, and the free cationic group not involved in the electrostatic interaction is reduced, thereby reducing the interaction with the negatively charged powder.

The polysaccharide derivative of the present invention is particularly effective for a fabric made of a hydrophobic fiber, but is not limited thereto. Further, it is preferable to treat the fabric in the presence of an anionic surfactant, but the treatment is not limited thereto, and it is confirmed that the adsorption to the fabric is exhibited even in the absence of an anionic surfactant.

< hydroxyalkylated polysaccharide >

The polysaccharide derivative of the present invention is a hydroxyalkylated polysaccharide in which a cationic group and a hydrocarbon group (R) are bonded to a weight average molecular weight of 1 to 74 million.

Furthermore, the hydroxyalkylated polysaccharide is a hydroxyethylated polysaccharide or a hydroxypropylated polysaccharide. Further, the hydroxyalkylation refers to monohydroxyalkylation.

As the hydroxyalkylated polysaccharide used in the present invention, there may be mentioned: the polysaccharide may be a polysaccharide such as cellulose, guar gum, or starch, or a polysaccharide having a substituent such as a methyl group introduced therein, and may further have at least one selected from the group consisting of a hydroxyethyl group and a hydroxypropyl group.

Examples of hydroxyalkylated polysaccharides include: hydroxyethyl cellulose, hydroxyethyl guar, hydroxyethyl starch, hydroxypropyl cellulose, hydroxypropyl guar, hydroxypropyl starch, hydroxyethyl methyl cellulose, hydroxyethyl methyl guar, hydroxyethyl methyl starch, hydroxypropyl methyl cellulose, hydroxypropyl methyl guar, hydroxypropyl methyl starch, and the like.

The polysaccharide is preferably cellulose or guar gum, more preferably cellulose.

The hydroxyalkylated polysaccharide is preferably hydroxyethyl cellulose, hydroxypropyl cellulose, more preferably hydroxyethyl cellulose.

(hydroxyalkyl)

In the present invention, the hydroxyalkylated polysaccharide introduces hydroxyalkyl groups into the polysaccharide. The hydroxyalkyl group is selected from at least one of a hydroxyethyl group and a hydroxypropyl group, more preferably has only a hydroxyethyl group or a hydroxypropyl group, and still more preferably has only a hydroxyethyl group. The hydroxyalkylated polysaccharide may have both a hydroxyethyl group and a hydroxypropyl group, preferably has only one of them, and more preferably has only a hydroxyethyl group.

The degree of substitution of the hydroxyalkyl group is preferably 0.1 or more, more preferably 0.5 or more, even more preferably 1 or more, and even more preferably 1.5 or more, from the viewpoint of solubility in water. From the viewpoint of cleaning performance, the cleaning agent is preferably 10 or less, more preferably 8 or less, even more preferably 5 or less, even more preferably 3 or less, and even more preferably 2.5 or less.

The degree of substitution of the hydroxyalkyl group is preferably 0.1 or more and 10 or less, more preferably 0.5 or more and 8 or less, further preferably 1 or more and 5 or less, further preferably 1.5 or more and 3 or less, and further preferably 1.5 or more and 2.5 or less, from the viewpoint of solubility in water and cleaning performance.

The degree of substitution of a hydroxyalkyl group refers to the degree of substitution of any group, for example, when only a hydroxyethyl group or a hydroxypropyl group is present. On the other hand, the term "having both a hydroxyethyl group and a hydroxypropyl group" means the total of the substitution degree of the hydroxyethyl group and the substitution degree of the hydroxypropyl group.

In the present invention, the degree of substitution of the X group means the molar average degree of substitution (MS) of the X group, and means the average number of moles of substitution per 1 mole of the X group of monosaccharide units constituting the main chain of the polysaccharide derivative or polysaccharide. For example, in the case where the hydroxyalkylated polysaccharide is hydroxyethyl cellulose, "the degree of substitution of hydroxyethyl groups" means the average number of moles of (bonded) hydroxyethyl groups introduced per 1 mole of anhydroglucose unit.

The hydroxyalkylated polysaccharide of the present invention may have a glycerin group as a substituent, but the cleaning performance tends to be lowered by introducing a glycerin group. Therefore, from the viewpoint of obtaining high cleaning performance, the degree of substitution of the glyceryl groups is preferably less than 0.5, more preferably less than 0.1, and even more preferably 0, that is, no glyceryl groups are present.

The hydroxyalkylated polysaccharide having a glycerin group is obtained by allowing a glycerating agent to act on a polysaccharide, and examples of the glycerating agent include: glycidyl alcohol; 3-halo-1, 2-propanediol such as 3-chloro-1, 2-propanediol and 3-bromo-1, 2-propanediol; glycerol; glycerol carbonate. Among these, glycidol is preferable from the viewpoints of not by-producing a salt and reactivity.

(weight average molecular weight)

In the present invention, the weight average molecular weight of the hydroxyalkylated polysaccharide is 1 ten thousand or more, preferably 3 ten thousand or more, more preferably 5 ten thousand or more, further preferably 7 ten thousand or more, further preferably 10 ten thousand or more, and further preferably 13 ten thousand or more, from the viewpoint of improving the cleaning performance.

Further, from the viewpoint of recontamination prevention performance, it is 74 ten thousand or less, preferably 72 ten thousand or less, more preferably 65 ten thousand or less, further preferably 60 ten thousand or less, further preferably 50 ten thousand or less, further preferably 40 ten thousand or less, further preferably 30 ten thousand or less, further preferably 20 ten thousand or less, and from the viewpoint of flowability of the preparation, it is preferably 19 ten thousand or less, more preferably 18 ten thousand or less, further preferably 17 ten thousand or less, further preferably 16 ten thousand or less.

The weight average molecular weight of the hydroxyalkylated polysaccharide is 1 ten thousand or more and 74 ten thousand or less, preferably 1 ten thousand or more and 72 ten thousand or less, more preferably 1 ten thousand or more and 65 ten thousand or less, even more preferably 3 ten thousand or more and 60 ten thousand or less, even more preferably 5 ten thousand or more and 50 ten thousand or less, even more preferably 7 ten thousand or more and 40 ten thousand or less, even more preferably 10 ten thousand or more and 30 ten thousand or less, and even more preferably 13 ten thousand or more and 20 ten thousand or less, from the viewpoint of improving the cleaning performance and the viewpoint of preventing the recontamination performance.

From the viewpoint of improving the cleaning performance and the fluidity of the preparation, it is preferably 1 ten thousand or more and 19 ten thousand or less, more preferably 3 ten thousand or more and 18 ten thousand or less, further preferably 5 ten thousand or more and 17 ten thousand or less, further preferably 7 ten thousand or more and 16 ten thousand or less, and further preferably 13 ten thousand or more and 16 ten thousand or less.

In the present invention, the weight average molecular weight of the hydroxyalkylated polysaccharide is preferably 13 ten thousand or more and 19 ten thousand or less, more preferably 13 ten thousand or more and 18 ten thousand or less, more preferably 13 ten thousand or more and 17 ten thousand or less, and more preferably 13 ten thousand or more and 16 ten thousand or less, from the viewpoint of improving the cleaning performance, preventing the recontamination performance, and from the viewpoint of the flowability of the preparation.

The weight average molecular weight of the hydroxyalkylated polysaccharide was measured by the method described in the examples. In addition, when the hydroxyalkylated polysaccharide is used as a product, the nominal value of the manufacturing company may be used.

< cationic group >

The polysaccharide derivative of the present invention is obtained by introducing a cationic group into the above-mentioned hydroxyalkylated polysaccharide. Here, the cationic group means a tertiary amine which can be converted into a quaternary ammonium salt by addition of a quaternary ammonium salt or a proton, and a quaternary ammonium salt thereof (quaternary ammonium cation).

Degree of substitution (MS) with respect to cationic group_C) From the viewpoint of improving the cleaning performance, it is preferably 0.001 or more, and more preferably0.005 or more, more preferably 0.01 or more, still more preferably 0.02 or more, still more preferably 0.05 or more, and still more preferably 0.07 or more.

The degree of substitution of the cationic group is preferably 1 or less, more preferably 0.5 or less, even more preferably 0.4 or less, even more preferably 0.35 or less, even more preferably 0.3 or less, even more preferably 0.25 or less, even more preferably 0.2 or less, and even more preferably 0.15 or less, from the viewpoint of the anti-redeposition property.

Degree of substitution (MS) with respect to cationic group_C) From the viewpoint of improving the cleaning performance and the anti-redeposition performance, it is preferably 0.001 to 1, more preferably 0.001 to 0.5, even more preferably 0.001 to 0.4, even more preferably 0.001 to 0.35, even more preferably 0.001 to 0.3, even more preferably 0.005 to 0.3, even more preferably 0.01 to 0.25, even more preferably 0.02 to 0.2, even more preferably 0.05 to 0.2, and even more preferably 0.07 to 0.15.

The degree of substitution of the cationic group was measured by the method described in examples.

The cationic group introduced into the hydroxyalkylated polysaccharide is preferably represented by the following formula (2-1) or formula (2-2) as a whole.

[ chemical formula 1]

(formula (2-1) and formula (2-2) wherein R²¹～R²³Each independently represents a hydrocarbon group having 1 to 24 carbon atoms, X-represents an anion, t represents an integer of 0 to 3, and represents a bonding position with a group obtained by removing a hydrogen atom from a hydroxyl group of a hydroxyalkylated polysaccharide)

R²¹～R²³Each independently represents a hydrocarbon group having 1 to 24 carbon atoms, preferably a linear or branched hydrocarbon group having 1 to 4 carbon atoms. Specifically, the following can be exemplified: methyl radicalEthyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl. Among these, methyl or ethyl is preferred, and R is more preferred²¹～R²³All are methyl or ethyl, and more preferably R²¹～R²³All are methyl groups.

In the formulae (2-1) and (2-2), t represents an integer of 0 to 3, preferably an integer of 1 to 3, more preferably 1 or 2, and still more preferably 1.

X^-Denotes an anion, which is the counterion of the quaternary ammonium cation. Specifically, the following can be exemplified: an alkylsulfate ion having 1 to 3 carbon atoms, a sulfate ion, a phosphate ion, a carboxylate ion having 1 to 3 carbon atoms (a formate ion, an acetate ion, a propionate ion), and a halide ion.

Among these, X is X from the viewpoint of ease of production and ease of raw material acquisition^-Preferably, the metal halide is at least one selected from the group consisting of alkylsulfate ions, sulfate ions and halide ions having 1 to 3 carbon atoms, and more preferably a halide ion. As the halide ion, there can be mentioned: the water-soluble polysaccharide derivative to be obtained is preferably one or more selected from the group consisting of a chloride ion and a bromide ion, and more preferably a chloride ion.

X^-May be a single one or two or more.

< hydrocarbyl (R) >

The polysaccharide derivative of the present invention introduces a hydrocarbon group (R) into a hydroxyalkylated polysaccharide.

The degree of substitution (MS) of the hydrocarbon group (R) in the polysaccharide derivative of the present invention_R) From the viewpoint of improving the cleaning performance, it is preferably 0.001 or more, more preferably 0.003 or more, further preferably 0.005 or more, further preferably 0.008 or more, further preferably 0.01 or more, further preferably 0.015 or more. The degree of substitution (MS) of the hydrocarbon group (R) in the polysaccharide derivative of the present invention_R) From the viewpoint of solubility in water, 1 or more is preferableThe content is more preferably 0.5 or less, even more preferably 0.3 or less, even more preferably 0.1 or less, even more preferably 0.08 or less, even more preferably 0.06 or less, even more preferably 0.05 or less, even more preferably 0.04 or less, even more preferably 0.03 or less.

Degree of substitution (MS) with respect to the hydrocarbon group (R)_R) From the viewpoint of improving the cleaning performance and the solubility in water, it is preferably 0.001 or more and 1 or less, more preferably 0.001 or more and 0.5 or less, even more preferably 0.001 or more and 0.3 or less, even more preferably 0.001 or more and 0.1 or less, even more preferably 0.001 or more and 0.05 or less, even more preferably 0.003 or more and 0.04 or less, even more preferably 0.005 or more and 0.03 or less, even more preferably 0.008 or more and 0.03 or less, even more preferably 0.01 or more and 0.03 or less, and even more preferably 0.015 or more and 0.03 or less.

In the present invention, the hydrocarbon group (R) is preferably an aliphatic hydrocarbon group, which may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, more preferably a saturated aliphatic hydrocarbon group, yet more preferably a linear or branched alkyl group, and yet more preferably a linear alkyl group.

Preferred degree of substitution (MS) of cationic group_C) Degree of substitution (MS) with hydrocarbon group (R)_R) The combinations of (a) and (b) are as follows.

The degree of substitution (MS) of the cationic group is preferred_C) Is 0.001-1 inclusive, and the degree of substitution (MS) of the hydrocarbon group (R)_R) 0.001 to 1 inclusive; more preferably the degree of substitution (MS) of the cationic group_C) Is 0.001-0.5 inclusive, and the degree of substitution (MS) of the hydrocarbon group (R)_R) 0.001 to 0.3 inclusive; further preferably the degree of substitution (MS) of the cationic group_C) Is 0.001-0.4 inclusive, and the degree of substitution (MS) of the hydrocarbon group (R)_R) 0.001 to 0.1 inclusive; more preferably, the degree of substitution (MS) of the cationic group_C) Is 0.001-0.4 inclusive, and the degree of substitution (MS) of the hydrocarbon group (R)_R) 0.001 to 0.05 inclusive; more preferably a cationic groupDegree of substitution of the group (MS)_C) Is 0.005-0.3, and the degree of substitution (MS) of the hydrocarbon group (R)_R) 0.003 to 0.04 inclusive; more preferably, the degree of substitution (MS) of the cationic group_C) Is 0.02-0.2 inclusive, and the degree of substitution (MS) of the hydrocarbon group (R)_R) 0.008 to 0.03 inclusive; more preferably, the degree of substitution (MS) of the cationic group_C) Is 0.07-0.15 inclusive, and the degree of substitution (MS) of the hydrocarbon group (R)_R) Is 0.015 to 0.03 inclusive.

The number of carbon atoms of the hydrocarbon group (R) is 2 or more, preferably 4 or more, more preferably 6 or more, further preferably 8 or more, and further preferably 10 or more, from the viewpoint of improving the cleaning performance. From the viewpoint of improving the cleaning performance, it is preferably 22 or less, more preferably 18 or less, further preferably 16 or less, further preferably 15 or less, further preferably 14 or less.

The carbon number of the hydrocarbon group (R) is preferably 2 or more and 22 or less, more preferably 4 or more and 22 or less, further preferably 4 or more and 18 or less, further preferably 6 or more and 16 or less, further preferably 8 or more and 15 or less, further preferably 8 or more and 14 or less, and further preferably 10 or more and 14 or less, from the viewpoint of improving the cleaning performance.

Degree of substitution (MS) of hydrocarbon group (R) having 2 or more carbon atoms_R) Degree of substitution (MS) of C9 or more hydrocarbon group (R) in (A)_9R)(MS_9R/MS_R) From the viewpoint of improving the cleaning performance, it is preferably 0.25 or more and 1 or less, more preferably 0.5 or more and 1 or less, further preferably 0.9 or more and 1 or less, and may be 1.

In the present invention, the hydrocarbon group (R) is bonded directly or through a hydrocarbon group having an oxygen atom to a group obtained by removing a hydrogen atom from a hydroxyl group of a hydroxyalkylated polysaccharide.

That is, the hydrocarbon group (R) is preferably bonded to a group obtained by removing a hydrogen atom from a hydroxyl group of the hydroxyalkylated polysaccharide through a linking group Z represented by the following formula (1).

[ chemical formula 2]

＊-Z-R (1)

(in the formula (1), Z represents a single bond or a divalent hydrocarbon group having an oxygen atom, R represents a hydrocarbon group having 2 or more carbon atoms, and represents a bonding position with a group obtained by removing a hydrogen atom from a hydroxyl group of a hydroxyalkylated polysaccharide)

Z represents a single bond or a divalent hydrocarbon group having an oxygen atom. The hydrocarbon group is preferably an alkylene group, and a part of methylene groups of the alkylene group may be substituted with an ether bond or carbonyl carbon (-C (═ O) -), or a part of hydrogen atoms of the alkylene group may be substituted with a hydroxyl group, an alkyl group, or a hydroxyalkyl group. The divalent hydrocarbon group having an oxygen atom preferably contains an ester group and/or an ether group, and more preferably contains an ether group. Here, when Z is a divalent hydrocarbon group having an oxygen atom, Z is composed of only a carbon atom, a hydrogen atom, and an oxygen atom, and does not include a nitrogen atom, for example.

When Z is a divalent hydrocarbon group having an oxygen atom (hereinafter, also referred to as a hydrocarbon group (Z)), the hydrocarbon group (Z) preferably has a group derived from an epoxy group or a group derived from an oxyglycidyl group, and more preferably has a group derived from an oxyglycidyl group from the viewpoint of cleaning performance. When Z is a divalent hydrocarbon group having an oxygen atom, the number of carbons of the hydrocarbon group is preferably 1 or more and 6 or less, more preferably 1 or more and 3 or less.

R is defined so that the number of carbons of the hydrocarbon group is the largest. Therefore, the atom in Z bonded to R in formula (1) is, for example, an oxygen atom, a carbonate carbon, a carbon atom substituted with a hydroxyl group, a carbon atom substituted with a hydroxyalkyl group.

In the formula (1), R represents a hydrocarbon group having 2 or more carbon atoms, preferably an aliphatic hydrocarbon group, which may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, more preferably a saturated aliphatic hydrocarbon group, still more preferably a linear or branched alkyl group, and yet more preferably a linear alkyl group.

In the formula (1), the carbon number of R is 2 or more, preferably 4 or more, more preferably 6 or more, further preferably 8 or more, and further preferably 10 or more, from the viewpoint of improving the cleaning performance. From the viewpoint of improving the cleaning performance, it is preferably 22 or less, more preferably 18 or less, further preferably 16 or less, further preferably 15 or less, further preferably 14 or less.

The group represented by the formula (1) is more preferably a group represented by any one of the following formulae (1-1-1) to (1-4).

[ chemical formula 3]

(formula (1-1-1) to (1-4) wherein R¹¹And R¹²Each independently represents an alkylene group having 2 to 4 carbon atoms, R represents a hydrocarbon group having 2 or more carbon atoms, represents a bonding position with a group obtained by removing a hydrogen atom from a hydroxyl group of a hydroxyalkylated polysaccharide, and n1 represents-R¹¹Average molar number of addition of O-, n2 represents-R¹²The average molar number of addition of-O-, n1 and n2 being 0 to 30 inclusive.

In the formulae (1-1-1) to (1-4), R is the same as R in the formula (1), and the preferable embodiment is the same. Z in formula (1) is a group obtained by removing R from formula (1-1-1) to formula (1-4).

In the formulae (1-1-1) to (1-4), R¹¹And R¹²Each independently represents an alkylene group having 2 to 4 carbon atoms, preferably an ethylene group or a propylene group having 2 or 3 carbon atoms. In the presence of a plurality of R¹¹And R¹²In the case of (3), they may be the same or different. n1 and n2 are 0 or more and 30 or less, preferably 0 or more and 20 or less, more preferably 0 or more and 10 or less, further preferably 0 or more and 5 or less, and may be 0.

The formula (1-1-1) and the formula (1-1-2) are groups derived from glycidyl ((poly) alkyleneoxy) hydrocarbon ethers, and are groups in which Z in the formula (1) is derived from an oxyglycidyl group or a (poly) alkyleneoxyglycidyl group. The group represented by the formula (1-1-1) or the formula (1-1-2) is obtained by using a glycidyl ((poly) alkyleneoxy) hydrocarbon ether, preferably a glycidyl ((poly) alkyleneoxy) alkyl ether, more preferably a glycidyl alkyl ether, as an introducing agent for the hydrocarbon group (R) (hereinafter, also referred to as "hydrophobizing agent").

The formulae (1-2-1) and (1-2-2) are groups in which Z in the formula (1) is derived from an epoxy group. The groups represented by the formulae (1-2-1) and (1-2-2) can be obtained by using a terminal epoxidized hydrocarbon, preferably a terminal epoxidized alkane, as an introducing agent for the hydrocarbon group (R).

Further, the formula (1-3) is a case where the hydrocarbon group (R) is directly bonded to a group obtained by removing a hydrogen atom from a hydroxyl group of the hydroxyalkylated polysaccharide. The group represented by the formula (1-3) is obtained by using a halogenated hydrocarbon as a hydrophobizing agent.

The formula (1-4) contains a group wherein Z is derived from a carboxyl group or the like. The group represented by the formula (1-4) is obtained by using R- (O-R)¹²)_n2-C(＝O)-OH、R-(O-R¹²)_n2-C (═ O) -a (a represents a halogen atom), R- (O-R)¹²)_n2-C(＝O)-O-C(＝O)-(R¹²-O)_n2-R and the like are obtained as an introducing agent for the hydrocarbon group (R).

Among these, the group represented by the formula (1-1-1), the formula (1-1-2), the formula (1-2-1) or the formula (1-2-2) is preferable, and the group represented by the formula (1-1-1) or the formula (1-1-2) is more preferable, from the viewpoint of no side production of salts during synthesis of the polysaccharide derivative and cleaning performance.

In the present invention, the degree of substitution (MS) of the hydrocarbon group (R) of the polysaccharide derivative_R) Degree of substitution with cationic group (MS)_C) Ratio of (MS)_R/MS_C) From the viewpoint of the cleaning performance and the anti-redeposition performance, the cleaning performance is preferably 0.001 or more, more preferably 0.005 or more, even more preferably 0.01 or more, and even more preferably 0.05 or more, and from the same viewpoint, the cleaning performance is preferably 1 or less, more preferably 0.8 or less, even more preferably 0.6 or less, even more preferably 0.5 or less, and even more preferably 0.3 or less.

Degree of substitution (MS) with respect to hydrocarbyl groups (R) of polysaccharide derivatives_R) Degree of substitution with cationic group (MS)_C) Ratio of (MS)_R/MS_C) From the viewpoint of cleaning performance and anti-redeposition performance, it is preferably 0.001 to 1, more preferably 0.005 to 0.8, more preferably 0.005 to 0.6, even more preferably 0.01 to 0.5, more preferably 0.05 to 0.5, and even more preferably 0.05 to 0.3.

In the present invention, the hydrocarbon group (R) and the cationic group are preferably bonded to oxygen atoms of different hydroxyl groups of the hydroxyalkylated polysaccharide from the viewpoint of cleaning performance and anti-redeposition performance. That is, it is preferable that the polysaccharide derivative not have a hydrocarbon group (R) and a cationic group in one side chain. Preferably, the hydrocarbon group (R) and the cationic group are bonded to different side chains of the polysaccharide derivative.

In the present invention, the polysaccharide derivative may have an anionic group, and the substitution degree (MS) of the anionic group in the polysaccharide derivative may be_A) Degree of substitution with cationic group (MS)_C) Ratio of (MS)_A/MS_C) From the viewpoint of cleaning performance, it is preferably 3 or less, more preferably 2 or less, further preferably 1.7 or less, further preferably 1.5 or less, further preferably 1 or less, further preferably 0.5 or less, further preferably 0.1 or less, and may be 0 or more, further preferably 0.

Degree of substitution (MS) with respect to anionic groups in polysaccharide derivatives_A) From the viewpoint of cleaning performance, it is preferably 0.3 or less, more preferably 0.1 or less, even more preferably 0.03 or less, even more preferably less than 0.01, even more preferably 0.001 or less, and may be 0 or more, even more preferably 0.

When the polysaccharide derivative has an anionic group, examples of the anionic group include: sulfate ester groups, sulfonic acid groups, carboxymethyl groups, and the like.

The carboxymethylation reaction (the reaction of introducing a carboxymethyl group) is carried out by reacting a monohalogenated acetic acid and/or a metal salt thereof with a hydroxyalkylated polysaccharide in the presence of a basic compound.

Specific examples of monohalogenated acetic acids and monohalogenated acetic acid metal salts include: monochloroacetic acid, monochloroacetic acid sodium, monochloroacetic acid potassium, monobromoacetic acid sodium, monobromoacetic acid potassium, etc. These monohaloacetic acids and metal salts thereof may be used alone or in combination of two or more.

Preferred degrees of substitution (MS) of the hydrocarbyl groups (R) of the polysaccharide derivatives_R) Degree of substitution with cationic group (MS)_C) Ratio of (MS)_R/MS_C) And degree of substitution (MS) with anionic group_A) Degree of substitution with cationic group (MS)_C) Ratio of (MS)_A/MS_C) The combinations of (a) and (b) are as follows.

The degree of substitution (MS) of the hydrocarbon group (R) of the polysaccharide derivative is preferred_R) Degree of substitution with cationic group (MS)_C) Ratio of (MS)_R/MS_C) Is 0.001-1 inclusive, and has a degree of substitution (MS) of an anionic group_A) Degree of substitution with cationic group (MS)_C) Ratio of (MS)_A/MS_C) Is 3 or less; more preferably (MS)_R/MS_C) Is 0.005 to 0.8 inclusive and (MS)_A/MS_C) Is 1.5 or less; more preferably (MS)_R/MS_C) Is 0.005 to 0.6 inclusive and (MS)_A/MS_C) Is 1 or less; more preferably (MS)_R/MS_C) Is 0.05 to 0.5 inclusive and (MS)_A/MS_C) Is less than 0.5; more preferably (MS)_R/MS_C) Is 0.05 to 0.3 inclusive and (MS)_A/MS_C) Is 0.3 or less.

From the above viewpoint, the substitution degree (MS) of the cationic group is preferable_C) A degree of substitution (MS) of the hydrocarbon group of 0.001 to 1 inclusive_R) A degree of substitution (MS) of the hydrocarbon group (R) of 0.001 to 1 inclusive_R) Degree of substitution with cationic group (MS)_C) Ratio of (MS)_R/MS_C) Is 0.001-1 inclusive, and has a degree of substitution (MS) of an anionic group_A) Degree of substitution with cationic group (MS)_C) Ratio of (MS)_A/MS_C) Is 3 or less;

more preferably the degree of substitution (MS) of the cationic group_C) A degree of substitution (MS) of the hydrocarbon group of 0.001 to 0.5 inclusive_R) A degree of substitution (MS) of the hydrocarbon group (R) of 0.001 to 0.3 inclusive_R) Degree of substitution with cationic group (MS)_C) Ratio of (MS)_R/MS_C) Is 0.005-0.8, and has a degree of substitution (MS) of anionic groups_A) Degree of substitution with cationic group (MS)_C) Ratio of (MS)_A/MS_C) Is 1.5 or less;

further preferably the degree of substitution of the cationic group(s) (ii)MS_C) A degree of substitution (MS) of the hydrocarbon group of 0.001 to 0.4 inclusive_R) A degree of substitution (MS) of the hydrocarbon group (R) of 0.001 to 0.1 inclusive_R) Degree of substitution with cationic group (MS)_C) Ratio of (MS)_R/MS_C) Is 0.005-0.6, and has a degree of substitution (MS) of anionic groups_A) Degree of substitution with cationic group (MS)_C) Ratio of (MS)_A/MS_C) Is 1 or less;

more preferably, the degree of substitution (MS) of the cationic group_C) A degree of substitution (MS) of the hydrocarbon group (R) of 0.005 to 0.3 inclusive_R) A degree of substitution (MS) of the hydrocarbon group (R) of 0.003 to 0.04 inclusive_R) Degree of substitution with cationic group (MS)_C) Ratio of (MS)_R/MS_C) Is 0.05 to 0.5 inclusive, and has a degree of substitution (MS) of an anionic group_A) Degree of substitution with cationic group (MS)_C) Ratio of (MS)_A/MS_C) And 0.5 or less.

Preferred embodiments of the polysaccharide derivative of the present invention include the following polysaccharide derivatives: which has a cationic group and a hydrocarbon group (R) having 4 to 15 carbon atoms and has a degree of substitution (MS) of the cationic group_C) A degree of substitution (MS) of the hydrocarbon group of 0.001 to 0.4 inclusive_R) The weight average molecular weight of the hydroxyl-alkylated polysaccharide is from 1 to 74 ten thousand, the weight average molecular weight of the hydroxyl-alkylated polysaccharide is from 0.001 to 0.05, the hydrocarbon group (R) is bonded to a group obtained by removing a hydrogen atom from a hydroxyl group of the hydroxyl-alkylated polysaccharide directly or through a hydrocarbon group which may have an oxygen atom, and the hydroxyl-alkylated polysaccharide is a hydroxyethyl-or hydroxypropyl-alkylated polysaccharide.

Another preferred embodiment of the polysaccharide derivative of the present invention is a polysaccharide derivative selected from the group consisting of: the hydroxyalkylated polysaccharide has a cationic group and a hydrocarbon group (R) bonded to a group obtained by removing a hydrogen atom from a hydroxyl group of a hydroxyalkylated polysaccharide through a linking group comprising an ether group, and is a hydroxyethylated polysaccharide or a hydroxypropylated polysaccharide, wherein the hydroxyalkylated polysaccharide has a weight average molecular weight of 1 to 74 million.

Another preferred embodiment of the polysaccharide derivative of the present invention is a polysaccharide derivative selected from the group consisting of: the hydroxyalkylated polysaccharide has a cationic group and a hydrocarbon group (R) having 2 or more carbon atoms, wherein the hydrocarbon group (R) is bonded to a group obtained by removing a hydrogen atom from a hydroxyl group of a hydroxyalkylated polysaccharide directly or through a linking group (excluding the cationic group), and the weight average molecular weight of the hydroxyalkylated polysaccharide is 1 to 19 ten thousand. Here, the linking group (excluding the cationic group) includes the above-mentioned hydrocarbon group having an oxygen atom, amide group, urea group, and the like.

< use >)

The polysaccharide derivative of the present invention can inhibit the firm adhesion of oily dirt such as sebum dirt to a fabric by treating the fabric such as clothes, can improve the detergency of sebum dirt during washing, and can inhibit the re-contamination of the fabric by re-adhesion of carbon powder during washing.

The polysaccharide derivative of the present invention is preferably added to a detergent composition for clothing. By treating clothes in advance before dressing, it is expected that firm adhesion of sebum dirt is suppressed and the cleaning property of sebum dirt during cleaning is improved during use such as dressing. The detergent composition for clothing may contain the polysaccharide derivative of the present invention as a component thereof, and may be added thereto, and is not particularly limited.

The polysaccharide derivative of the present invention has a concentration in an aqueous solution when treating a fabric such as clothes of preferably 0.01 mg/L or more, more preferably 0.1 mg/L or more, even more preferably 0.3 mg/L or more, from the viewpoint of cleaning performance and anti-redeposition performance, and is preferably 10,000 mg/L or less, more preferably 1,000 mg/L or less, even more preferably 500 mg/L or less, and even more preferably 100 mg/L or less from the viewpoint of economy.

[ Process for producing polysaccharide derivative ]

< hydroxyalkylated polysaccharide >

The hydroxyalkylated polysaccharide is obtained by reacting a polysaccharide with a hydroxyalkylating agent in the presence of a basic compound.

Hereinafter, the case where the polysaccharide is cellulose will be described as an example, but the present invention is not limited thereto. Since cellulose generally has high crystallinity and lacks reactivity, it is preferable to perform treatment for reducing crystallinity and improving reactivity before the reaction.

Examples of the method for producing hydroxyalkylated cellulose include the following methods (i) to (iii).

Method (i): the activation method generally referred to as alkalization or mercerization is a method in which a raw material cellulose is mixed with a large amount of water and a large excess amount of an alkali metal hydroxide to obtain alkali cellulose, and then reacted with a hydroxyalkylating agent.

Method (ii): for the cellulose, for example, a solvent such as dimethyl sulfoxide containing tetrabutylammonium fluoride, dimethyl sulfoxide containing paraformaldehyde, and dimethylacetamide containing lithium chloride, and an encyclopedia and editor of "cellulose: the society of cellulose, press: a method comprising dissolving a raw material cellulose in a cellulose-soluble solvent described in Kokuku Kogyo, Macromol. chem. Phys.201,627-631(2000), etc., and then reacting the raw material cellulose with a hydroxyalkylating agent.

Method (iii): unlike the method (i) or (ii), a powdery or cotton-like raw material cellulose is reacted with a hydroxyalkylating agent in the presence of an alkali by using an excessive amount of an alkali or a special solvent capable of dissolving cellulose.

The hydroxyalkylating agent, cationizing agent, hydrophobizing agent, and activating method used as raw materials for producing the polysaccharide derivative will be described below.

(Hydroxyalkylating agent)

Specific examples of the hydroxyalkylating agent used for producing the polysaccharide derivative of the present invention include: alkylene oxides, alkyl glycidyl ethers, alkyl halohydrin ethers, and the like. Among these, from the viewpoint of not generating a salt during the reaction, one or more selected from alkylene oxides and alkyl glycidyl ethers are preferable, and alkylene oxides are more preferable.

The hydroxyalkylating agent is preferably at least one selected from the group consisting of ethylene oxide and propylene oxide, and more preferably ethylene oxide.

The hydroxyalkylated polysaccharide is commercially available, and a hydroxyalkylated polysaccharide obtained from a commercial site can be used.

Specifically, examples of the hydroxyethylcellulose include Natrosol series (Ashland corporation). In addition, hydroxyethyl cellulose and hydroxypropyl cellulose are also available from: shin Yue Chemical industry Co., Ltd, Dow Chemical company, Japan Cao Da Kao, Sumitomo Seiki Kao, three-crystal Kao, Daicel FineChem, Tokyo Kaisha, etc.

< cationizing agent >

Examples of the cationizing agent used for producing the polysaccharide derivative of the present invention include: and a compound represented by the following formula (3) or (4).

[ chemical formula 4]

In the formulae (3) and (4), R²¹～R²³And preferred embodiments thereof are the same as those of R of the above formulae (2-1) and (2-2)²¹～R²³The same is true. t and preferred embodiments thereof are the same as those of the above-mentioned formulae (2-1) and (2-2). X^-And preferred embodiments thereof are the same as those of X in the above formulae (2-1) and (2-2)^-The same is true. A represents a halogen atom. R²¹～R²³May be the same or different.

Specific examples of the compound represented by the above formula (3) or (4) include: each chloride, bromide or iodide of glycidyl trimethylammonium, glycidyl triethylammonium, glycidyl tripropylammonium; or the respective chlorides of 3-chloro-2-hydroxypropyltrimethylammonium, 3-chloro-2-hydroxypropyltriethylammonium, or 3-chloro-2-hydroxypropyltripropylammonium; each bromide of 3-bromo-2-hydroxypropyltrimethylammonium, 3-bromo-2-hydroxypropyltriethylammonium, or 3-bromo-2-hydroxypropyltripropylammonium; or 3-iodo-2-hydroxypropyltrimethylammonium, 3-iodo-2-hydroxypropyltriethylammonium, or 3-iodo-2-hydroxypropyltripropylammonium.

Among these, from the viewpoint of easiness of obtaining raw materials and chemical stability, chlorides or bromides selected from glycidyl trimethylammonium or glycidyl triethylammonium; chlorides of 3-chloro-2-hydroxypropyltrimethylammonium or 3-chloro-2-hydroxypropyltriethylammonium; 3-bromo-2-hydroxypropyl trimethylammonium chloride or 3-bromo-2-hydroxypropyl triethylammonium bromide, more preferably at least one compound selected from glycidyl trimethyl ammonium chloride and 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, and still more preferably glycidyl trimethyl ammonium chloride.

These cationizing agents may be used alone or in combination of two or more.

The amount of the cationizing agent to be used is determined in consideration of the desired degree of substitution (MS) of the cationic group_C) The reaction yield may be appropriately selected, and from the viewpoint of water solubility of the polysaccharide derivative and obtaining the effect of the present invention, it is preferably 0.01 mol or more, more preferably 0.03 mol or more, further preferably 0.05 mol or more, and further preferably 0.1 mol or more, relative to 1 mol of the constituent monosaccharide unit of the hydroxyalkylated polysaccharide, and from the viewpoint of the above and the manufacturing cost of the polysaccharide derivative, it is preferably 30 mol or less, more preferably 25 mol or less, further preferably 10 mol or less, further preferably 1 mol or less, and further preferably 0.5 mol or less.

The cationizing agent may be added in one step, intermittently, or continuously.

< introduction agent for a hydrocarbon group (R) >

The introduction agent (hydrophobizing agent) of the hydrocarbon group (R) used for producing the polysaccharide derivative of the present invention may be one which can introduce the group represented by the above formula (1).

Examples of the introducing agent capable of introducing the groups represented by the above formulae (1-1-1) and (1-1-2) include: a compound represented by the following formula (5) or (6).

[ chemical formula 5]

In the formulae (5) and (6), R and its preferenceThe same manner as that of R in the above formula (1). A represents a halogen atom, preferably a chlorine atom. R¹¹And preferred embodiments thereof are the same as those of R of the above-mentioned formulae (1-1-1) and (1-1-2)¹¹And its preferred mode is the same. N1 and preferred embodiments thereof are the same as those of n1 of the above formulae (1-1-1) and (1-1-2) and preferred embodiments thereof.

Specific examples of the compound represented by the above formula (5) include: glycidyl ethers having an alkyl group such as ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, hexadecyl glycidyl ether, heptadecyl glycidyl ether, and octadecyl glycidyl ether; glycidyl ethers having an alkenyl group such as butenyl glycidyl ether, pentenyl glycidyl ether, hexenyl glycidyl ether, heptenyl glycidyl ether, octenyl glycidyl ether, nonenyl glycidyl ether, decenyl glycidyl ether, undecenyl glycidyl ether, dodecenyl glycidyl ether, tridecenyl glycidyl ether, tetradecenyl glycidyl ether, pentadecenyl glycidyl ether, hexadecenyl glycidyl ether, heptadecenyl glycidyl ether, and octadecenyl glycidyl ether, and the like. Among these, alkyl glycidyl ethers having a hydrocarbon group of 5 to 25 carbon atoms such as lauryl glycidyl ether and cetyl glycidyl ether are preferable.

Specific examples of the compound represented by the above formula (6) include: 3-halo-2-hydroxypropyl alkyl ether having a hydrocarbon group of 5 to 25 carbon atoms such as 3-chloro-2-hydroxypropyl-dodecyl ether.

Among these, the compound represented by the above formula (5) is preferable from the viewpoint of no side production of salts when the hydrophobizing agent reacts with the hydroxyalkylated polysaccharide, and the viewpoint of easiness of obtaining the hydrophobizing agent and chemical stability.

These may be used alone or in combination of two or more.

Examples of the introducing agent capable of introducing the groups represented by the above formulae (1-2-1) and (1-2-2) include: and a compound represented by the following formula (7) or (8).

[ chemical formula 6]

In the formulae (7) and (8), R and preferred embodiments thereof are the same as those of the formula (1). A represents a halogen atom, preferably a chlorine atom.

Specific examples of the compound represented by the above formula (7) include: 1, 2-alkylene oxides having a hydrocarbon group of 4 to 24 carbon atoms such as 1, 2-cyclohexene oxide, 1, 2-heptane oxide, 1, 2-tetradecane oxide, and 1, 2-octadecane oxide. Specific examples of the compound represented by the above formula (8) include: 1-halo-2-hydroxyalkanes having a hydrocarbon group of 4 to 24 carbon atoms such as 1-chloro-2-hydroxytetradecane.

Among these, the compound represented by the above formula (7) is preferable from the viewpoint of no side production of salts when the hydrophobizing agent reacts with the hydroxyalkylated polysaccharide, and the viewpoint of easiness of obtaining the hydrophobizing agent and chemical stability.

These may be used alone or in combination of two or more.

Examples of the hydrophobizing agent into which the group represented by the above formula (1-3) can be introduced include: and a compound represented by the following formula (9).

[ chemical formula 7]

A-R (9)

In formula (9), R and preferred embodiments thereof are the same as those of formula (1) above. A represents a halogen atom, preferably a chlorine atom.

Specific examples of the compound represented by the above formula (9) include: halogenated alkanes having the desired carbon number described above.

Examples of the hydrophobizing agent into which the group represented by the above formula (1-4) can be introduced include: and compounds represented by the following formulae (10) to (12).

[ chemical formula 8]

In formulae (10) to (12), R and preferred embodiments thereof are the same as those of formula (1). A represents a halogen atom, preferably a chlorine atom.

In the formulae (10) to (12), R¹²N2 and preferred embodiments thereof and R of the formula (1-4)¹²And n2 are the same.

Specific examples of the compounds represented by the above formulae (10) to (12) include: fatty acid having the above-mentioned required carbon number, fatty acid halide, fatty acid anhydride.

The amount of the hydrophobizing agent to be used is determined in consideration of the desired degree of substitution (MS) of the hydrocarbon group (R)_R) The reaction yield may be appropriately selected, and from the viewpoint of water solubility of the polysaccharide derivative and obtaining the effect of the present invention, it is preferably 0.01 mol or more, and more preferably 0.03 mol or more, based on 1 mol of the constituent monosaccharide unit of the hydroxyalkylated polysaccharide, and from the viewpoint of the above and the viewpoint of the production cost of the polysaccharide derivative, it is preferably 5 mol or less, more preferably 3 mol or less, further preferably 1 mol or less, further preferably 0.5 mol or less, and further preferably 0.2 mol or less.

The hydrophobizing agent may be added in any of a single step, a batch step, and a continuous step.

< method for producing polysaccharide derivative >

In the method for producing a polysaccharide derivative of the present invention, it is preferable that the hydroxyalkylated polysaccharide is reacted with the cationizing agent and the agent for introducing a hydrocarbon group (R) (hydrophobizing agent) to introduce a cationic group and a hydrocarbon group (R).

In the method for producing a polysaccharide derivative of the present invention, it is more preferable that the hydrocarbon group (R) having 2 or more carbon atoms is introduced into the hydroxyalkylated polysaccharide having a weight average molecular weight of 1 to 74 ten thousand, and then reacted with the cationizing agent, from the viewpoints of ease of production and transparency of the obtained polysaccharide derivative. That is, it is more preferable that the hydrophobizing agent is reacted with a hydroxyalkylated polysaccharide having a weight average molecular weight of 1 to 74 ten thousand, and then a hydrocarbon group (R) having 2 or more carbon atoms is introduced, and then the resulting mixture is reacted with the cationizing agent to introduce a cationic group.

In the method for producing a polysaccharide derivative of the present invention, from the viewpoint of ease of production and transparency of the polysaccharide derivative to be obtained, it is more preferable to use a method for producing a polysaccharide derivative in which the aforementioned hydrophobizing agent is reacted with a hydroxyalkylated polysaccharide in the presence of a basic compound to introduce a hydrocarbon group (R) having 2 or more carbon atoms and then reacted with a cationizing agent without a washing step to introduce a cationic group.

These reactions are preferably all carried out in the presence of a basic compound. Examples of the basic compound used in this reaction include: alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide; alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide; tertiary amine compounds such as trimethylamine and triethylamine. Among these, from the viewpoint of the reaction rate of the introduction reaction, an alkali metal hydroxide or an alkaline earth metal hydroxide is preferable, an alkali metal hydroxide is more preferable, and sodium hydroxide and potassium hydroxide are even more preferable. These basic compounds may be used alone or in combination of two or more.

The method of adding the basic compound is not particularly limited, and the basic compound may be added at once or in portions. The basic compound may be added in a solid state or may be added after being made into an aqueous solution.

In the introduction reaction of the cationic group and the hydrocarbon group, the amount of the basic compound used for each is preferably 0.01 mol or more, more preferably 0.05 mol or more, and even more preferably 0.1 mol or more, with respect to 1 mol of the monosaccharide unit constituting the raw material polysaccharide (1 mol of anhydroglucose unit (AGU) in the case where the raw material polysaccharide is cellulose), from the viewpoint of the reaction selectivity of the reactant, and is preferably 10 mol or less, more preferably 5 mol or less, and even more preferably 3 mol or less, even more preferably 2 mol or less, even more preferably 1.0 mol or less, and even more preferably 0.8 mol or less, and even more preferably 0.5 mol or less from the same viewpoint.

The preferable amount of the basic compound used in the case where the cationic group introduction reaction and the hydrocarbon group introduction reaction are simultaneously carried out is also the same as the amount of the basic compound used in each of the cationic group introduction reaction and the hydrocarbon introduction reaction.

When the basic compound used in the hydroxyalkyl group introduction reaction, the cationic group introduction reaction, or the hydrocarbon group (R) introduction reaction is a polybasic base such as an alkaline earth metal hydroxide, the preferable range of the amount of the compound used is a range obtained by dividing the preferable amount of the basic compound in each reaction by the valence number of the polybasic base. For example, in the case where the basic compound used is calcium hydroxide (dibasic base), the amount of calcium hydroxide is preferably 0.005 mol or more, more preferably 0.025 mol or more, and even more preferably 0.05 mol or more, and from the same viewpoint of reaction selectivity, preferably 5 mol or less, more preferably 2.5 mol or less, even more preferably 1.5 mol or less, more preferably 1 mol or less, more preferably 0.5 mol or less, more even more preferably 0.4 mol or less, and even more preferably 0.25 mol or less, relative to 1 mol of AGU of the raw material cellulose.

That is, the basic compound is preferably 0.01 molar equivalent or more, more preferably 0.05 molar equivalent or more, further preferably 0.1 molar equivalent or more, preferably 10 molar equivalents or less, more preferably 5 molar equivalents or less, further preferably 3 molar equivalents or less, more preferably 2 molar equivalents or less, further more preferably 1 molar equivalent or less, further more preferably 0.8 molar equivalents or less, and further more preferably 0.5 molar equivalents or less, to 1 mole of the constituent monosaccharide unit of the hydroxyalkylated polysaccharide (in the case where the hydroxyalkylated polysaccharide is a hydroxyalkylated cellulose, to 1 mole of anhydroglucose unit (AGU) of the raw material cellulose).

The molar equivalent of the basic compound is the same as the number of moles when the basic compound is a monobasic basic compound such as sodium hydroxide, and is a value obtained by multiplying the number of moles by the valence when the basic compound is a dibasic basic compound such as calcium hydroxide.

The molar equivalent ratio of the basic compound to the cationizing agent (basic compound/cationizing agent) is preferably 0.1 or more, more preferably 0.5 or more, from the viewpoint of reactivity, and preferably 2 or less, more preferably 1.8 or less, from the viewpoint of improving the transparency of the obtained polysaccharide derivative. In the case where the cationizing agent is polyvalent, the same calculation is performed.

In the present invention, the hydroxyalkyl cellulose can be obtained by reacting powdered cellulose or cotton-like cellulose with the above-mentioned hydroxyalkylating agent to thereby carry out an introduction reaction of a hydroxyalkyl group.

Hereinafter, the introduction reaction of a hydroxyalkyl group (hydroxyalkylation reaction), the introduction reaction of a cationic group (cationization reaction), and the introduction reaction of a hydrocarbon group (R) (hydrophobization reaction) are also collectively referred to as "reactions in the production of polysaccharide derivatives".

In each reaction in the production of the polysaccharide derivative, the form of each of the hydroxyalkylating agent, cationizing agent and introduction agent of the hydrocarbon group (R) is not particularly limited. When the hydroxyalkylating agent, the cationizing agent and the hydrocarbon group-introducing agent are in a liquid state, they may be used as they are, or they may be used in a form diluted with a good solvent for the hydroxyalkylating agent, the cationizing agent and the hydrocarbon group-introducing agent such as water or a non-aqueous solvent.

As the nonaqueous solvent for dilution, there may be mentioned: generally used lower alcohols having 3 to 4 carbon atoms in the secondary or tertiary form, i.e., isopropanol and t-butanol; ketones having 3 to 6 carbon atoms such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ethers such as tetrahydrofuran, 1, 4-dioxane, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether; aprotic polar solvents such as dimethyl sulfoxide, and the like.

In the above-mentioned method (ii), each reaction in the production of the polysaccharide derivative is carried out by dissolving the raw material cellulose in a solvent which is used for dissolving the cellulose in the reaction, but in the methods (i) and (iii), the reaction may be carried out in the presence of a nonaqueous solvent from the viewpoint of the reaction yield of the hydroxyalkylating agent, the cationizing agent and the hydrocarbon group-introducing agent. As the nonaqueous solvent, the same nonaqueous solvents as described above can be used.

The cleaning step may be provided between the introduction reaction (hydrophobization reaction) of the hydrocarbon group (R) and the introduction reaction (cationization reaction) of the cationic group, but is preferably not provided from the viewpoint of ease of production. By setting the molar ratio of the basic compound to the cationizing agent (basic compound/cationizing agent) within the above range, the cationizing reaction can be performed without removing an excessive amount of the basic compound by a washing step after the hydrophobizing reaction. The washing step is a step of washing the reaction intermediate into which the hydrocarbon group (R) is introduced with a solvent such as hot water, isopropyl alcohol, or acetone to remove the basic compound as a salt from the unreacted introduction agent of the hydrocarbon group (R) or by neutralization. After the washing step, a basic compound may be added after filtration or drying to perform a cationization reaction.

Examples of the apparatus used for each reaction in the production of the polysaccharide derivative include: mixers such as flasks, SUS reaction tanks, and stirrable lady mixers; or a mixer such as a so-called kneader used for kneading powders, high-viscosity substances, resins, and the like.

The reaction temperature in each reaction in the production of the polysaccharide derivative is preferably 0 ℃ or higher, more preferably 20 ℃ or higher, and still more preferably 30 ℃ or higher, from the viewpoint of the reaction rate. Further, the decomposition of the hydroxyalkylating agent, cationizing agent or hydrocarbon group-introducing agent is preferably 200 ℃ or lower, more preferably 100 ℃ or lower.

The reaction temperature (in the hydrophobization reaction) for introducing the hydrocarbon group is preferably 55 ℃ or more, more preferably 60 ℃ or more from the viewpoint of reactivity, and is preferably 200 ℃ or less, more preferably 100 ℃ or less from the viewpoint of decomposition inhibition.

The reaction temperature for the reaction with the cationizing agent is preferably 20 ℃ or higher, more preferably 30 ℃ or higher, and still more preferably 40 ℃ or higher from the viewpoint of reactivity, and is preferably less than 55 ℃, more preferably 53 ℃ or lower, and still more preferably 51 ℃ or lower from the viewpoint of transparency of the obtained polysaccharide derivative.

In the production of polysaccharide derivatives, each reaction is preferably carried out in an inert gas atmosphere such as nitrogen gas, as required, from the viewpoint of suppressing coloration and the decrease in molecular weight of the main chain derived from monosaccharide units.

After the reaction is completed, the basic compound may be neutralized with an acid. In the case where the hydroxyalkylation reaction, cationization reaction and introduction reaction of a hydrocarbon group are separately performed, neutralization may be performed between the respective reactions, but from the viewpoint of suppressing the formation of a neutralized salt, it is preferable to perform the neutralization after all the reactions have been completed. As acids, it is possible to use: inorganic acids such as sulfuric acid, hydrochloric acid, and phosphoric acid; and organic acids such as acetic acid and lactic acid.

The polysaccharide derivative obtained after completion of all reactions in the production of the polysaccharide derivative may be subjected to fractionation by filtration or the like as necessary, or may be washed with hot water, aqueous isopropanol, aqueous acetone solvent or the like to remove unreacted hydroxyalkylating agent, cationizing agent, alkyl group-introducing agent, by-product organisms derived from these reactants, and salts by-produced by neutralization or the like. Further, as a purification method, a usual purification method such as reprecipitation purification, centrifugal separation, dialysis, or the like can be used.

The present invention also discloses the following <1> to <63 >.

<1> a polysaccharide derivative which is at least 1 selected from the following (A) and (B).

(A) The method comprises the following steps A polysaccharide derivative having a cationic group and a hydrocarbon group (R) having 2 or more carbon atoms, the hydrocarbon group (R) being bonded directly or via a hydrocarbon group having an oxygen atom to a group obtained by removing a hydrogen atom from a hydroxyl group of a hydroxyalkylated polysaccharide, the hydroxyalkylated polysaccharide being a hydroxyethylated polysaccharide or a hydroxypropylated polysaccharide, the hydroxyalkylated polysaccharide having a weight average molecular weight of 1 to 74 ten thousand;

(B) the method comprises the following steps The polysaccharide derivative has a cationic group and a hydrocarbon group (R) having 2 or more carbon atoms, the hydrocarbon group (R) is bonded to a group obtained by removing a hydrogen atom from a hydroxyl group of a hydroxyalkylated polysaccharide directly or via a linking group (excluding the cationic group), and the hydroxyalkylated polysaccharide has a weight average molecular weight of 1 to 19 ten thousand.

<2>According to<1>The polysaccharide derivative wherein the degree of substitution (MS) of the cationic group is_C) Preferably 0.001 or more, more preferably 0.005 or more, further preferably 0.01 or more, further preferably 0.02 or more, further preferably 0.05 or more, and further preferably 0.07 or more.

<3>According to<1>Or<2>The polysaccharide derivative wherein the degree of substitution (MS) of the cationic group is_C) Preferably 1 or less, more preferably 0.5 or less, further preferably 0.4 or less, further preferably 0.35 or less, further preferably 0.3 or less, further preferably 0.25 or less, further preferably 0.2 or less, further preferably 0.15 or less.

<4>According to<1>～<3>The polysaccharide derivative according to any one of the above, wherein the degree of substitution (MS) of the cationic group is_C) Preferably 0.001 or more and 1 or less, more preferably 0.001 or more and 0.5 or less, further preferably 0.001 or more and 0.4 or less, further preferably 0.001 or more and 0.35 or less, further preferably 0.001 or more and 0.3 or less, further preferably 0.005 or more and 0.3 or less, further preferably 0.01 or more and 0.25 or less, further preferably 0.02 or more and 0.2 or less, further preferably 0.05 or less and 0.2 or less, further preferably 0.07 or more and 0.15 or less.

<5>According to<1>～<4>The polysaccharide derivative according to any one of the above, wherein the degree of substitution (MS) of the hydrocarbon group (R)_R) Preferably 0.001 or more, more preferably 0.003 or more, further preferably 0.005 or more, further preferably 0.008 or more, further preferably 0.01 or more, and further preferably 0.015 or more.

<6>According to<1>～<5>The polysaccharide derivative according to any one of the above, wherein the degree of substitution (MS) of the hydrocarbon group (R)_R) Preferably 1 or less, more preferably0.5 or less, more preferably 0.3 or less, still more preferably 0.1 or less, still more preferably 0.08 or less, still more preferably 0.06 or less, still more preferably 0.05 or less, still more preferably 0.04 or less, still more preferably 0.03 or less.

<7>According to<1>～<6>The polysaccharide derivative according to any one of the above, wherein the degree of substitution (MS) of the hydrocarbon group (R)_R) Preferably 0.001 or more and 1 or less, more preferably 0.001 or more and 0.5 or less, further preferably 0.001 or more and 0.3 or less, further preferably 0.001 or more and 0.1 or less, further preferably 0.001 or more and 0.05 or less, further preferably 0.003 or more and 0.05 or less, more preferably 0.003 or more and 0.04 or less, further preferably 0.005 or more and 0.03 or less, further preferably 0.008 or more and 0.03 or less, further preferably 0.01 or more and 0.03 or less, and further preferably 0.015 or more and 0.03 or less.

<8>According to<1>～<3>The polysaccharide derivative according to any one of the above, wherein: degree of substitution (MS) of cationic group_C) A degree of substitution (MS) of the hydrocarbon group (R) of 0.001 to 1 inclusive_R) 0.001 to 1 inclusive; more preferably: degree of substitution (MS) of cationic group_C) Is 0.001-0.5 inclusive and has a degree of substitution (MS) of the hydrocarbon group (R)_R) 0.001 to 0.3 inclusive; further preferred are: degree of substitution (MS) of cationic group_C) A degree of substitution (MS) of the hydrocarbon group (R) of 0.001 to 0.4 inclusive_R) 0.001 to 0.1 inclusive; even more preferred are: degree of substitution (MS) of cationic group_C) A degree of substitution (MS) of the hydrocarbon group (R) of 0.001 to 0.4 inclusive_R) 0.001 to 0.05 inclusive; even more preferred are: degree of substitution (MS) of cationic group_C) Is 0.005-0.3 and the degree of substitution (MS) of the hydrocarbon group (R)_R) 0.003 to 0.04 inclusive; even more preferred are: degree of substitution (MS) of cationic group_C) A degree of substitution of the hydrocarbon group (R) of 0.02 to 0.2 inclusive(MS_R) 0.008 to 0.03 inclusive; even more preferred are: degree of substitution (MS) of cationic group_C) Is 0.07-0.15 inclusive and has a degree of substitution (MS) of the hydrocarbon group (R)_R) Is 0.015 to 0.03 inclusive.

<9> the polysaccharide derivative according to any one of <1> to <8>, wherein the hydrocarbon group (R) has 2 or more, preferably 4 or more, more preferably 6 or more, further preferably 8 or more, and still further preferably 10 or more carbon atoms.

<10> the polysaccharide derivative according to any one of <1> to <9>, wherein the number of carbon atoms of the hydrocarbon group (R) is preferably 22 or less, more preferably 18 or less, still more preferably 16 or less, still more preferably 15 or less, and still more preferably 14 or less.

<11> the polysaccharide derivative according to any one of <1> to <10>, wherein the number of carbon atoms of the hydrocarbon group (R) is preferably 2 or more and 22 or less, more preferably 4 or more and 22 or less, further preferably 4 or more and 18 or less, further preferably 4 or more and 16 or less, further preferably 4 or more and 15 or less, further preferably 8 or more and 14 or less, and further preferably 10 or more and 14 or less.

<12> the polysaccharide derivative according to any one of <1> to <11>, wherein the divalent hydrocarbon group having an oxygen atom preferably contains an ester group and/or an ether group, more preferably an ether group.

<13>A polysaccharide derivative having a cationic group and a hydrocarbon group (R) having 4 to 15 carbon atoms, wherein the degree of substitution (MS) of the cationic group is_C) A degree of substitution (MS) of the hydrocarbon group of 0.001 to 0.4 inclusive_R) The weight average molecular weight of the hydroxyl-alkylated polysaccharide is from 1 to 74 ten thousand, the weight average molecular weight of the hydroxyl-alkylated polysaccharide is from 0.001 to 0.05, the hydrocarbon group (R) is bonded directly or via a hydrocarbon group having an oxygen atom to a group obtained by removing a hydrogen atom from a hydroxyl group of the hydroxyl-alkylated polysaccharide, and the hydroxyl-alkylated polysaccharide is a hydroxyethyl-alkylated polysaccharide or a hydroxypropyl-alkylated polysaccharide.

<14>According to<13>Among the polysaccharide derivatives, preferred are: degree of substitution (MS) of cationic group_C) Is 0.005-0.3 and the degree of substitution (MS) of the hydrocarbon group (R)_R) 0.003 to 0.04 inclusive; more preferably: degree of substitution (MS) of cationic group_C) A degree of substitution (MS) of the hydrocarbon group (R) of 0.02 to 0.2 inclusive_R) 0.008 to 0.03 inclusive; further preferred are: degree of substitution (MS) of cationic group_C) Is 0.07-0.15 inclusive and has a degree of substitution (MS) of the hydrocarbon group (R)_R) Is 0.015 to 0.03 inclusive.

<15> the polysaccharide derivative according to <13> or <14>, wherein the number of carbon atoms of the hydrocarbon group (R) is preferably 8 or more and 15 or less, more preferably 8 or more and 14 or less, and still more preferably 10 or more and 14 or less.

<16> the polysaccharide derivative according to any one of <13> to <15>, wherein the hydrocarbon group having an oxygen atom preferably contains an ester group and/or an ether group, more preferably an ether group.

<17> a polysaccharide derivative which is a polysaccharide derivative having a cationic group and a hydrocarbon group (R) bonded to a group obtained by removing a hydrogen atom from a hydroxyl group of a hydroxyalkylated polysaccharide through a linking group comprising an ether group, wherein the hydroxyalkylated polysaccharide is a hydroxyethylated polysaccharide or a hydroxypropylated polysaccharide, and the hydroxyalkylated polysaccharide has a weight average molecular weight of 1 to 74 million.

<18>According to<17>Among the polysaccharide derivatives, preferred are: degree of substitution (MS) of cationic group_C) A degree of substitution (MS) of the hydrocarbon group (R) of 0.001 to 1 inclusive_R) 0.001 to 1 inclusive; more preferably: degree of substitution (MS) of cationic group_C) Is 0.001-0.5 inclusive and has a degree of substitution (MS) of the hydrocarbon group (R)_R) 0.001 to 0.3 inclusive; further preferred are: degree of substitution (MS) of cationic group_C) A degree of substitution (MS) of the hydrocarbon group (R) of 0.001 to 0.4 inclusive_R) 0.001 to 0.1 inclusive; it is further preferred that: degree of substitution (MS) of cationic group_C) A degree of substitution (MS) of the hydrocarbon group (R) of 0.001 to 0.4 inclusive_R) 0.001 to 0.05 inclusive; even more preferred are: degree of substitution (MS) of cationic group_C) Is 0.005-0.3 and the degree of substitution (MS) of the hydrocarbon group (R)_R) 0.003 to 0.04 inclusive; even more preferred are: degree of substitution (MS) of cationic group_C) A degree of substitution (MS) of the hydrocarbon group (R) of 0.02 to 0.2 inclusive_R) 0.008 to 0.03 inclusive; even more preferred are: degree of substitution (MS) of cationic group_C) Is 0.07-0.15 inclusive and has a degree of substitution (MS) of the hydrocarbon group (R)_R) Is 0.015 to 0.03 inclusive.

<19> the polysaccharide derivative according to <17> or <18>, wherein the number of carbon atoms of the hydrocarbon group (R) is preferably 2 or more and 22 or less, more preferably 4 or more and 18 or less, further preferably 4 or more and 16 or less, further preferably 4 or more and 15 or less, further preferably 8 or more and 14 or less, and further preferably 10 or more and 14 or less.

<20> the polysaccharide derivative according to any one of <1> to <19>, wherein the hydroxyalkylated polysaccharide further has at least 1 selected from the group consisting of hydroxyethyl groups and hydroxypropyl groups, in addition to a polysaccharide such as cellulose, guar gum, starch, or the like, or a polysaccharide having a methyl group as a substituent introduced therein.

<21> the polysaccharide derivative according to any one of <1> to <20>, wherein the hydroxyalkylated polysaccharide is hydroxyethyl cellulose, hydroxyethyl guar, hydroxyethyl starch, hydroxypropyl cellulose, hydroxypropyl guar, hydroxypropyl starch, hydroxyethyl methyl cellulose, hydroxyethyl methyl guar, hydroxyethyl methyl starch, hydroxypropyl methyl cellulose, hydroxypropyl methyl guar or hydroxypropyl methyl starch.

<22> the polysaccharide derivative according to any one of <1> to <21>, wherein the polysaccharide is preferably cellulose or guar gum, more preferably cellulose.

<23> the polysaccharide derivative according to any one of <1> to <22>, wherein the degree of substitution with hydroxyalkyl groups is preferably 0.1 or more, more preferably 0.5 or more, still more preferably 1 or more, and still more preferably 1.5 or more.

<24> the polysaccharide derivative according to any one of <1> to <23>, wherein the degree of substitution with hydroxyalkyl groups is preferably 10 or less, more preferably 8 or less, still more preferably 5 or less, still more preferably 3 or less, and still more preferably 2.5 or less.

<25> the polysaccharide derivative according to any one of <1> to <24>, wherein the degree of substitution with hydroxyalkyl groups is preferably 0.1 or more and 10 or less, more preferably 0.5 or more and 8 or less, further preferably 1 or more and 5 or less, further preferably 1.5 or more and 3 or less, and further preferably 1.5 or more and 2.5 or less.

<26> the polysaccharide derivative according to any one of <1> to <25>, wherein the degree of substitution with a glyceryl group is preferably less than 0.5, more preferably less than 0.1, and still more preferably 0, that is, no glyceryl group is present.

<27> the polysaccharide derivative according to any one of <1> to <26>, wherein the hydroxyalkylated polysaccharide has a weight average molecular weight of 1 ten thousand or more, preferably 3 ten thousand or more, more preferably 5 ten thousand or more, further preferably 7 ten thousand or more, further preferably 10 ten thousand or more, and further preferably 13 ten thousand or more.

<28> the polysaccharide derivative according to any one of <1> to <27>, wherein the hydroxyalkylated polysaccharide has a weight average molecular weight of 74 ten thousand or less, preferably 72 ten thousand or less, more preferably 65 ten thousand or less, further preferably 60 ten thousand or less, further preferably 50 ten thousand or less, further preferably 40 ten thousand or less, further preferably 30 ten thousand or less, further preferably 20 ten thousand or less, preferably 19 ten thousand or less, further preferably 18 ten thousand or less, further preferably 17 ten thousand or less, and further preferably 16 ten thousand or less.

<29> the polysaccharide derivative according to any one of <1> to <28>, wherein the hydroxyalkylated polysaccharide has a weight average molecular weight of 1 to 74 million, preferably 1 to 72 million, more preferably 1 to 65 million, still more preferably 3 to 60 million, yet more preferably 5 to 50 million, yet more preferably 7 to 40 million, yet more preferably 10 to 30 million, yet more preferably 13 to 20 million, preferably 13 to 19 million, more preferably 13 to 18 million, still more preferably 13 to 17 million, and yet more preferably 13 to 16 million.

<30> the polysaccharide derivative according to any one of <1> to <29>, wherein the cationic group is represented by formula (2-1) or formula (2-2).

[ chemical formula 9]

(in the formulae (2-1) and (2-2), R²¹～R²³Each independently represents a hydrocarbon group having 1 to 24 carbon atoms, X^-Represents an anion, and t represents an integer of 0 to 3 inclusive, and represents a position bonded to a group obtained by removing a hydrogen atom from a hydroxyl group of the hydroxyalkylated polysaccharide. )

<31>According to<30>The polysaccharide derivative, wherein, in the formulae (2-1) and (2-2), R²¹～R²³Each independently represents a hydrocarbon group having 1 to 24 carbon atoms, preferably a linear or branched hydrocarbon group having 1 to 4 carbon atoms, more preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, a methyl group or an ethyl group, still more preferably R²¹～R²³Are each methyl or ethyl, more preferably R²¹～R²³Are all methyl.

<32> the polysaccharide derivative according to any one of <1> to <31>, wherein the hydrocarbon group (R) and a group obtained by removing a hydrogen atom from a hydroxyl group of the hydroxyalkylated polysaccharide are bonded via a linking group Z represented by the following formula (1).

[ chemical formula 10]

＊-Z-R (1)

(in formula (1), Z represents a single bond or a divalent hydrocarbon group having an oxygen atom, R represents a hydrocarbon group having 2 or more carbon atoms, and represents a position bonded to a group obtained by removing a hydrogen atom from a hydroxyl group of a hydroxyalkylated polysaccharide.)

<33> the polysaccharide derivative according to <32>, wherein the linking group Z in the formula (1) preferably has a group derived from an epoxy group or a group derived from an oxyglycidyl group, more preferably has a group derived from an oxyglycidyl group.

<34>According to<1>～<33>The polysaccharide derivative according to any one of the above, wherein the degree of substitution (MS) of the hydrocarbon group (R) of the polysaccharide derivative_R) Degree of substitution with cationic group (MS)_C) Ratio of (MS)_R/MS_C) Preferably 0.001 or more, more preferably 0.005 or more, further preferably 0.01 or more, and further preferably 0.05 or more.

<35>According to<1>～<34>The polysaccharide derivative according to any one of the above, wherein the degree of substitution (MS) of the hydrocarbon group (R) of the polysaccharide derivative_R) Degree of substitution with cationic group (MS)_C) Ratio of (MS)_R/MS_C) Preferably 1 or less, more preferably 0.8 or less, further preferably 0.6 or less, further preferably 0.5 or less, and further preferably 0.3 or less.

<36>According to<1>～<35>The polysaccharide derivative according to any one of the above, wherein the degree of substitution (MS) of the hydrocarbon group (R) of the polysaccharide derivative_R) Degree of substitution with cationic group (MS)_C) Ratio of (MS)_R/MS_C) Preferably 0.001 to 1, more preferably 0.005 to 0.8, further preferably 0.005 to 0.6, further preferably 0.01 to 0.5, further preferably 0.05 to 0.5, and further preferably 0.05 to 0.3.

<37>According to<1>～<36>The polysaccharide derivative according to any one of the above, wherein the degree of substitution (MS) of the anionic group is_A) Degree of substitution with cationic group (MS)_C) Ratio of (MS)_A/MS_C) Preferably 3 or less, more preferably 2 or less, further preferably 1.7 or less, further preferably 1.5 or less, further preferably 1 or less, further preferably 0.5 or less, further preferably 0.1 or less, and may be 0 or more, further preferably 0.

<38>According to<1>～<37>The polysaccharide derivative according to any one of the above, wherein the polysaccharide derivative optionally has an anionic group, and the substitution degree (MS) of the anionic group in the polysaccharide derivative_A) Preferably 0.3 or less, more preferably 0.1 or less, further preferably less than 0.01, further preferably 0.001 or less, and may be 0 or more, further preferably 0.

<39>According to<1>～<38>The polysaccharide derivative according to any one of the above, wherein: degree of substitution (MS) of hydrocarbyl groups (R) of polysaccharide derivatives_R) Degree of substitution with cationic group (MS)_C) Ratio of (MS)_R/MS_C) Is 0.001-1 inclusive and has a degree of substitution (MS) with an anionic group_A) Degree of substitution with cationic group (MS)_C) Ratio of (MS)_A/MS_C) Is 3 or less; more preferably: (MS)_R/MS_C) Is 0.005 to 0.8 inclusive and (MS)_A/MS_C) Is 1.5 or less; further preferred are: (MS)_R/MS_C) Is 0.005 to 0.6 inclusive and (MS)_A/MS_C) Is 1 or less; even more preferred are: (MS)_R/MS_C) Is 0.05 to 0.5 inclusive and (MS)_A/MS_C) Is less than 0.5; even more preferred are: (MS)_R/MS_C) Is 0.05 to 0.3 inclusive and (MS)_A/MS_C) Is 0.3 or less.

<40>According to<1>～<39>The polysaccharide derivative according to any one of the above, wherein the degree of substitution (MS) of the cationic group is_C) A degree of substitution (MS) of the hydrocarbon group of 0.001 to 0.5 inclusive_R) A hydrocarbon group (R) of 0.001 to 0.3 inclusiveDegree of substitution (MS)_R) Degree of substitution with cationic group (MS)_C) Ratio of (MS)_R/MS_C) Is 0.005-0.8 inclusive and has a degree of substitution (MS) with an anionic group_A) Degree of substitution with cationic group (MS)_C) Ratio of (MS)_A/MS_C) Is 1.5 or less.

<41>According to<1>～<40>The polysaccharide derivative according to any one of the above, wherein the degree of substitution (MS) of the cationic group is_C) A degree of substitution (MS) of the hydrocarbon group of 0.001 to 0.4 inclusive_R) A degree of substitution (MS) of the hydrocarbon group (R) of 0.001 to 0.1 inclusive_R) Degree of substitution with cationic group (MS)_C) Ratio of (MS)_R/MS_C) Is 0.005-0.6 inclusive, and has a degree of substitution (MS) of an anionic group_A) Degree of substitution with cationic group (MS)_C) Ratio of (MS)_A/MS_C) Is 1 or less.

<42>According to<1>～<41>The polysaccharide derivative according to any one of the above, wherein the degree of substitution (MS) of the cationic group is_C) A degree of substitution (MS) of the hydrocarbon group (R) of 0.005 to 0.3 inclusive_R) A degree of substitution (MS) of the hydrocarbon group (R) of 0.003 to 0.04 inclusive_R) Degree of substitution with cationic group (MS)_C) Ratio of (MS)_R/MS_C) Is 0.05 to 0.5 inclusive and has a degree of substitution (MS) with an anionic group_A) Degree of substitution with cationic group (MS)_C) Ratio of (MS)_A/MS_C) Is 0.5 or less.

<43> the polysaccharide derivative according to any one of <1> to <42>, wherein the concentration of the polysaccharide derivative in an aqueous solution at the time of treatment of the polysaccharide derivative is preferably 0.01 mg/L or more, more preferably 0.1 mg/L or more, still more preferably 0.3 mg/L or more.

<44> the polysaccharide derivative according to any one of <1> to <43>, wherein the concentration of the polysaccharide derivative in an aqueous solution at the time of treatment of the polysaccharide derivative is preferably 10000 mg/L or less, more preferably 1000 mg/L or less, still more preferably 500 mg/L or less, and still more preferably 100 mg/L or less.

<45> the polysaccharide derivative according to any one of <1> to <44>, which is obtained by reacting a hydroxyalkylated polysaccharide with a cationizing agent and a hydrophobizing agent, wherein the cationizing agent is at least 1 selected from the group consisting of compounds represented by the following formulae (3) and (4), and introducing a cationic group and a hydrocarbon group having 2 or more carbon atoms into the hydroxyalkylated polysaccharide.

[ chemical formula 11]

In the formulae (3) and (4), R²¹～R²³Each independently represents a hydrocarbon group having 1 to 24 carbon atoms, X^-Represents an anion, t represents an integer of 0 to 3 inclusive, and A represents a halogen atom. R²¹～R²³Optionally identical or different from each other.

<46> the polysaccharide derivative according to <45>, wherein, the cationizing agent is selected from the group consisting of glycidyl trimethylammonium, glycidyl triethylammonium, glycidyl tripropylammonium, each chloride, bromide or iodide, 3-chloro-2-hydroxypropyltrimethylammonium, 3-chloro-2-hydroxypropyltriethylammonium or 3-chloro-2-hydroxypropyltripropylammonium, 3-bromo-2-hydroxypropyltrimethylammonium, 3-bromo-2-hydroxypropyltriethylammonium, 3-bromo-2-hydroxypropyltripropylammonium, 3-iodo-2-hydroxypropyltrimethylammonium, 3-iodo-2-hydroxypropyltriethylammonium, and 3-iodo-2-hydroxypropyltripropylammonium.

<47> the polysaccharide derivative according to <45> or <46>, wherein the amount of the cationizing agent added is preferably 0.01 mol or more, more preferably 0.03 mol or more, further preferably 0.05 mol or more, and further preferably 0.1 mol or more based on 1 mol of the constituent monosaccharide units of the hydroxyalkylated polysaccharide.

<48> the polysaccharide derivative according to any one of <45> to <47>, wherein the amount of the cationizing agent added is preferably 30 moles or less, more preferably 25 moles or less, still more preferably 10 moles or less, still more preferably 1 mole or less, and still more preferably 0.5 moles or less based on 1 mole of the constituent monosaccharide unit of the hydroxyalkylated polysaccharide.

<49> the polysaccharide derivative according to any one of <1> to <48>, which is obtained by reacting a hydroxyalkylated polysaccharide with a cationizing agent and a hydrophobizing agent, wherein the hydroxyalkylated polysaccharide is obtained by introducing a cationic group and a hydrocarbon group having 2 or more carbon atoms into the hydroxyalkylated polysaccharide, and the hydrophobizing agent is at least 1 selected from the group consisting of compounds represented by the following formulae (5) and (6).

[ chemical formula 12]

In the formulae (5) and (6), R¹¹Each independently represents an alkylene group having 2 to 4 carbon atoms, R represents a hydrocarbon group having 2 or more carbon atoms, represents a position bonded to a group obtained by removing a hydrogen atom from a hydroxyl group of a hydroxyalkylated polysaccharide, and n1 represents-R¹¹N1 is 0 to 30 inclusive, and A represents a halogen atom.

<50> the polysaccharide derivative according to <49>, wherein the compound represented by the formula (5) or (6) is an alkyl-containing glycidyl ether such as ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, hexadecyl glycidyl ether, heptadecyl glycidyl ether, or octadecyl glycidyl ether; glycidyl ethers having an alkenyl group such as butenyl glycidyl ether, pentenyl glycidyl ether, hexenyl glycidyl ether, heptenyl glycidyl ether, octenyl glycidyl ether, nonenyl glycidyl ether, decenyl glycidyl ether, undecenyl glycidyl ether, dodecenyl glycidyl ether, tridecenyl glycidyl ether, tetradecenyl glycidyl ether, pentadecenyl glycidyl ether, hexadecenyl glycidyl ether, heptadecenyl glycidyl ether, and octadecenyl glycidyl ether, and the like.

<51> the polysaccharide derivative according to any one of <1> to <50>, which is obtained by reacting a hydroxyalkylated polysaccharide with a cationizing agent and a hydrophobizing agent, wherein the hydroxyalkylated polysaccharide is obtained by introducing a cationic group and a hydrocarbon group having 2 or more carbon atoms into the hydroxyalkylated polysaccharide, and the hydrophobizing agent is at least 1 selected from the group consisting of compounds represented by the following formulae (7) and (8).

[ chemical formula 13]

In the formulae (7) and (8), R represents a hydrocarbon group having 2 or more carbon atoms, and A represents a halogen atom.

<52> the polysaccharide derivative according to <51>, wherein the compound represented by the formula (7) is preferably a 1, 2-alkylene oxide having 4 to 24 carbon atoms, specifically 1, 2-epoxytetradecane or 1, 2-epoxyoctadecane, and the compound represented by the formula (8) is preferably a 1-halo-2-hydroxyalkane having 4 to 24 carbon atoms, specifically 1-chloro-2-hydroxytetradecane.

<53> the polysaccharide derivative according to any one of <49> to <52>, wherein the hydrophobizing agent is added in an amount of preferably 0.01 mol or more, more preferably 0.03 mol or more based on 1 mol of the constituent monosaccharide units of the hydroxyalkylated polysaccharide.

<54> the polysaccharide derivative according to any one of <49> to <53>, wherein the hydrophobizing agent is added in an amount of preferably 5 moles or less, more preferably 3 moles or less, further preferably 1 mole or less, further preferably 0.5 moles or less, and further preferably 0.2 moles or less based on 1 mole of the constituent monosaccharide unit of the hydroxyalkylated polysaccharide.

<55>According to<1>～<54>The polysaccharide derivative according to any one of the above, wherein the degree of substitution (MS) of the hydrocarbon group (R) having 2 or more carbon atoms_R) In (2), the degree of substitution (MS) of the hydrocarbon group (R) having 9 or more carbon atoms_9R)(MS_9R/MS_R) Preferably 0.25 to 1, more preferably 0.5 to 1, still more preferably 0.9 to 1, and still more preferably 1.

<56> the process for producing a polysaccharide derivative according to any one of <1> to <55>, wherein a hydrocarbon group (R) having 2 or more carbon atoms is introduced into a hydroxyalkylated polysaccharide having a weight average molecular weight of 1 to 74 million, and then the resultant is reacted with a cationizing agent.

<57> the process for producing a polysaccharide derivative according to <56>, wherein a hydrocarbon group (R) having 2 or more carbon atoms is introduced into a hydroxyalkylated polysaccharide in the presence of a basic compound, and then the resultant is preferably reacted with a cationizing agent without a washing step.

<58> the process for producing a polysaccharide derivative according to <57>, wherein the molar equivalent ratio of the alkali compound to the cationizing agent (alkali compound/cationizing agent) is preferably 0.1 or more, more preferably 0.5 or more.

<59> the process for producing a polysaccharide derivative according to <57> or <58>, wherein the molar equivalent ratio of the alkali compound to the cationizing agent (alkali compound/cationizing agent) is preferably 2 or less, more preferably 1.8 or less.

<60> the process for producing a polysaccharide derivative according to any one of <56> to <59>, wherein the reaction temperature for introducing the hydrocarbon group having 2 or more carbon atoms is preferably 55 ℃ or more, more preferably 60 ℃ or more.

<61> the process for producing a polysaccharide derivative according to any one of <56> to <60>, wherein the reaction temperature for introducing the hydrocarbon group having 2 or more carbon atoms is preferably 200 ℃ or less, more preferably 100 ℃ or less.

<62> the process for producing a polysaccharide derivative according to any one of <56> to <61>, wherein the reaction temperature for the reaction with the cationizing agent is preferably 20 ℃ or higher, more preferably 30 ℃ or higher, and still more preferably 40 ℃ or higher.

<63> the process for producing a polysaccharide derivative according to any one of <56> to <62>, wherein the reaction temperature for the reaction with the cationizing agent is preferably less than 55 ℃, more preferably 53 ℃ or less, and still more preferably 51 ℃ or less.

[ examples ]

The measurement methods used in examples and comparative examples are as follows.

[ measurement of degree of substitution (molar average degree of substitution (MS) ]

Pretreatment

After 1g of the powdery cellulose derivative was dissolved in 100g of water, the aqueous solution was added to a dialysis membrane (Spectra/Por, molecular weight 1,000) and dialyzed for 2 days. The obtained aqueous solution was freeze-dried using a freeze dryer (eyela, FDU1100) to obtain a purified cellulose derivative.

< calculation of cationic group Mass by Kjeldahl method >

200mg of the purified cellulose derivative was weighed out accurately, 10m L m sulfuric acid and a piece of Kay ingot (Merck)1 were added thereto, and thermal decomposition was carried out by a Kay decomposition apparatus (BUCHI K-432), after the decomposition was completed, 30m L m ion-exchanged water was added to the sample, and the nitrogen content (mass%) of the sample was determined by using an automatic Kay distillation apparatus (BUCHI K-370), whereby the mass of the cationic group was calculated.

< calculation of the Mass of a hydrocarbyl (alkyl) group by Zeisel's method >

Hereinafter, a method for calculating the mass of the alkyl group as the hydrocarbon group (R) will be described by taking a case of example 1 (lauryl glycidyl ether is used as an introducing agent of the hydrocarbon group) as an example. When other introducing agents are used, the measurement can be carried out by appropriately selecting a sample for calibration curve (e.g., an agent for introducing iodoalkane or hydrocarbon group).

200mg of the purified cellulose derivative and 220mg of adipic acid were weighed accurately and placed in a 10m L vial (Mighty Vial No.3), an internal standard solution (tetradecane/o-xylene 1/25(v/v))3m L and hydroiodic acid 3m L were added thereto and the mixture was fastened, and a sample for calibration curve to which 2, 4, or 9mg of 1-iodododecane was added instead of the cellulose derivative was prepared.

GC analysis conditions

Column Agilent HP-1 (length: 30m, thickness of liquid phase film: 0.25. mu. L, inner diameter: 32mm)

The split ratio is as follows: 20

Temperature of the pipe column: 100 ℃ (2min) → 10 ℃/min → 300 ℃ (15min)

Injector temperature: 300 deg.C

A detector: FID

Detector temperature: 330 deg.C

Injection quantity of 2 mu L

The mass of the alkyl group in the sample was determined from the detected amount of 1-iodododecane obtained by GC.

< measurement of hydroxyalkyl Mass >

The measurement of the mass of the alkyl group is carried out in the same manner as described above by quantifying the iodinated alkyl group derived from the hydroxyalkyl group.

< calculation of degree of substitution (molar average degree of substitution) of cationic group, alkyl group, and hydroxyalkyl group >

The substitution degree (MS) of the cationic group was calculated by calculating the mass of the hydroxyethyl cellulose (HEC) skeleton from the mass of the cationic group and the alkyl group as the hydrocarbon group (R) and the total sample mass, and converting the mass into the amount (mol) of each substance_C) And degree of substitution (MS) of alkyl group_R)。

The degree of substitution was calculated similarly for hydroxyalkyl groups.

< calculation of the mass of anionic group by atomic absorption spectrometry >

0.1g of the cellulose derivative obtained in examples 13 and 14 was collected, placed in a decomposition vessel, and wet-decomposed by adding sulfuric acid (for precision analysis, Wako pure chemical industries, Ltd.) 4m L, nitric acid (for atomic absorption analysis, Kanto chemical Co., Ltd.), and hydrogen peroxide (for atomic absorption analysis, Wako pure chemical industries, Ltd.) as appropriate, to prepare a sample measurement solution (the sulfuric acid content was also adjusted to the same degree as the calibration curve) by diluting the solution 25 times with a solution having a constant volume of 100m L using ultrapure water as a sample measurement stock solution.

Calibration Curve solutions A calibration curve solution was prepared by using a standard solution for atomic absorption analysis (Na: 1000 mg/L, 1000 mg/L, Kanto chemical Co., Ltd.) in an amount of 0.1 to 20 mg/L, and adding sulfuric acid to each solution so that the sulfuric acid concentration became 4%.

The prepared sample was passed through an ICP emission spectrometer and the Na content was measured under the following conditions.

(analysis conditions)

An analysis device: manufactured by Thermo Fisher Scientific, iCAP 6500Duo

Measurement wavelength: na 589.582nm

RF power: 950W

Cooling gas flow rate 12L/min

Nebulizer flow 0.70L/min

0.5L/min auxiliary gas

Pump flow rate: 50r.p.m

The mass of the anionic group was calculated by obtaining the Na content (mass%) of the sample.

< calculation of degree of substitution (molar average degree of substitution) of anionic group, cationic group, alkyl group and hydroxyalkyl group >

The degree of substitution (MS) of the anionic group was calculated by calculating the mass of the HEC skeleton from the mass of the anionic group, the masses of the cationic group and the alkyl group, and the total sample mass, and converting the masses into the amounts (mol) of the substances_A) Degree of substitution of cationic group (MS)_C) Anddegree of substitution (MS) of alkyl group_R). The degree of substitution was calculated similarly for hydroxyalkyl groups.

< calculation of the Mass of hydrophobic group (bonding type: ammonium group) by Kjeldahl method >

200mg of the cellulose derivative used in comparative example 4 was weighed out accurately, 10m L of sulfuric acid and a piece of Kevlar (Merck)1 were added thereto, and thermal decomposition was carried out using a Kevlar decomposition apparatus (BUCHI K-432), after the decomposition was completed, 30m L of ion-exchanged water was added to the sample, and the mass of the hydrophobic group (bonding type: ammonium group) was calculated by subtracting the mass of the cationic group derived from GMAC from the nitrogen content (mass%) of the sample using an automatic Kevlar distillation apparatus (BUCHI K-370).

< calculation of degree of substitution (molar average degree of substitution) of alkyl group (bonding type: ammonium group), cationic group, and hydroxyalkyl group >

The mass of the HEC skeleton was calculated from the mass of the alkyl group (bonding species: ammonium group), the mass of the cationic group, and the total sample mass, and the masses were converted into the amounts (mol) of the substances, respectively, to calculate the degree of substitution (MS) of the alkyl group (bonding species: ammonium group)_R-C) Degree of substitution of cationic group (MS)_C). The degree of substitution was calculated similarly for the hydroxyalkyl group.

[ measurement of weight average molecular weight ]

The weight average molecular weight of hydroxyethyl cellulose (HEC) was calculated by converting it into polyethylene glycol by GPC (gel permeation chromatography).

The measurement conditions are as follows.

Column TSKgel α -M

Eluent 50 mmol/L L iBr, 1% CH₃COOH, ethanol/water 3/7

A temperature: 40 deg.C

Flow rate 0.6m L/min

Example 1

(1) Synthesis of cellulose derivatives

Hydroxyethyl cellulose (HEC) (Ashland Co., Natrosol250JR, weight average molecular weight: 15 ten thousand, degree of substitution of hydroxyethyl group: 2.5)90g was put in a 1L separable flask, nitrogen gas was passed, 77.2g of ion-exchanged water and 414.5g of isopropyl alcohol (hereinafter, referred to as IPA) were added, the mixture was stirred at 200r.p.m. for 5 minutes, 10.9g of a 48% aqueous solution of sodium hydroxide was added, the mixture was further stirred for 15 minutes, 3.9g of lauryl glycidyl ether (L A-EP, manufactured by Nissan corporation) was added, alkylation reaction was carried out at 80 ℃ for 13 hours, glycidyl trimethyl ammonium chloride (hereinafter, referred to as "GMAC", SY-GTA80, manufactured by Kazakukan corporation) was further added, and neutralization reaction was carried out at 50 ℃ for 1.5 hours, and then 10.9g of a 90% aqueous solution of acetic acid was added, and the mixture was stirred for 30 minutes.

The obtained suspension was equally transferred to two 500m L centrifuge tubes, and centrifuged using a high speed cooling centrifuge (Nigri Kogyo, CR21G III), the supernatant was removed by decantation, an 85% IPA aqueous solution in an amount equal to the amount of the removed supernatant was added, and redispersed, and the operations of centrifugation and redispersion were repeated again, and after the 3 rd centrifugation, the precipitate was taken out, and the obtained precipitate was dried under reduced pressure at 80 ℃ for 12 hours using a vacuum dryer (Advantech, VR-420), and crushed using an Extreme mill (WARING, MX-1200XTM), thereby obtaining a powdery cellulose derivative.

(2-1) preparation of chemical fiber for cleaning evaluation

In a spiral tube of 100m L, a treatment liquid of the following composition 40m L and 5 pieces of polyester cloth (6cm × cm, polyester satin, manufactured by staining test materials co., ltd.). the treatment liquid on the polyester cloth was treated by horizontally reciprocating oscillation for 5 minutes at 300r.p.m. using an oscillator (model: SA300), after which the polyester cloth was dehydrated for 1 minute by a double tank washing machine (manufactured by hitachi corporation, PS-H45L type), next, ion exchange water for cleaning 40m L was put in the spiral tube of 100m L and the obtained polyester cloth, and the polyester cloth was washed for 3 minutes at 300r.p.m. using an oscillator, after which the polyester cloth was dehydrated for 1 minute by the double tank washing machine and naturally dried for 24 hours.

< composition of treatment liquid >

(A) Cellulose derivatives: 0 or 30mg/kg

(B) Surfactant (polyoxyethylene (3) lauryl ether sodium sulfate (trade name: Emal 20C)/polyoxyethylene (10) lauryl ether (trade name: Emulgen 110L) ═ 1/1(w/w) calculated by effective component) 80mg/kg

(2-2) preparation of stained cloth

A sample sebum artificial stain of 0.1m L, which was obtained by mixing 0.02% Sudan III with oleic acid, was uniformly applied to the polyester cloth (36 cm) prepared in the above (2-1)²) And dried at 40 ℃ for 1 hour using a constant temperature dryer (EYE L a, inc., accumator FMS).

(3) Cleaning test

The cleaning solution was prepared by diluting with ion-exchanged water so that the surfactant (sodium polyoxyethylene (3) lauryl ether sulfate/polyoxyethylene (10) lauryl ether) became 1/1(w/w)) to 150mg/kg, and in a 1L stainless steel beaker for cleaning test, 600m L of the cleaning solution and 5 pieces of the polyester cloth obtained in (2-2) above were put, and the polyester cloth was cleaned using a Terg-O-meter (manufactured by shanghai corporation, MS-8212) under conditions of 85r.p.m., 20 ℃ and 10 minutes, and the obtained polyester cloth was washed with a large amount of water, dehydrated by a two-tank washing machine, and then naturally dried for 24 hours.

[ evaluation of cleaning efficiency and cleaning efficiency improving Performance ]

The reflectance at 460nm of the polyester base cloth before the contamination and the reflectance at 460nm of the polyester cloth before and after the cleaning were measured by a colorimeter (manufactured by Nippon Denshoku industries Co., Ltd., SE-2000), and the cleaning ratio (%) was determined by the following equation.

Cleaning ratio (%) < 100 × [ (reflectance after cleaning-reflectance before cleaning)/(reflectance of original cloth-reflectance before cleaning) ]

The cleaning efficiency improvement performance (%) was determined from the difference in cleaning efficiency from the blank sample in which the component (A) was 0mg/kg in the above (2-1) by the following equation.

Cleaning ratio improving performance (%) (cleaning ratio (%) of component A30 mg/kg (cleaning ratio (%) of component A0 mg/kg)

[ evaluation of resistance to carbon redeposition ]

The cleaning solution 600m L was added with 20mg of carbon black (standard carbon black for asahi cleaning, manufactured by asahi carbon corporation) selected by japan oil chemical association, and irradiated with ultrasonic waves for 1 hour using an ultrasonic oscillator (UT206, manufactured by shoarp filtration SYSTEM), then the dispersion was transferred to a 1L stainless steel beaker of Terg-O-meter, and 5 pieces of polyester cloth obtained in the above (2-1) were put into the tank washer, and the polyester cloth was subjected to carbon recontamination treatment under conditions of 85r.p.m., 20 ℃, 10 minutes using the Terg-O-meter, and the obtained polyester cloth was washed with a large amount of water, dehydrated by a double tank washer, dried naturally for 24 hours, and measured for color difference between 1/1(w/w) and 1/1(w/w) for the polyester (10 minutes), and the recontamination prevention performance of the polyester cloth was found to be superior by the color difference (%) and the recontamination prevention performance of the polyester cloth was found to be superior.

Carbon recontamination prevention rate (%) -100 × (reflectance after recontamination/reflectance of original cloth)

[ evaluation of flowability of preparation ]

An aqueous solution (5m L) containing 20 mass% of a surfactant (polyoxyethylene (10) lauryl ether (trade name "Emulgen 110L", manufactured by kao corporation)) and 3 mass% of the above polysaccharide derivative as an active ingredient was prepared in a 10m L spiral tube (with a scale), and the solution was stirred with a stirrer for 24 hours (20 ℃).

The obtained solution was inverted up and down together with the spiral tube, and the fluidity was evaluated by visual observation.

The time for substantially all of the solution (90% or more) to move from the upper portion to the lower portion was measured.

The time for which substantially all of the solution (90% or more) moves from the upper portion to the lower portion is preferably within 5 seconds, more preferably within 3 seconds.

Examples 2 to 12 and comparative examples 1 to 3

The cellulose derivatives shown in table 1 were synthesized in the same manner as in example 1. Further, the cleaning performance, the anti-redeposition property, and the formulation flowability were evaluated in the same manner as in example 1.

Example 13

10g of the powdery cellulose derivative synthesized in example 1 was put in a 1L separable flask, nitrogen gas was passed through, 43.3g of IPA and 4.8g of ion-exchanged water were added, the mixture was stirred at 100r.p.m. for 5 minutes, then 5.4g of a 48% aqueous solution of sodium hydroxide was added, further stirring was carried out for 15 minutes, then 0.8g of sodium monochloroacetate (Wako pure chemical industries, Ltd.) was added, and a carboxymethylation reaction was carried out at 70 ℃ for 2.5 hours, and then 3.5g of acetic acid was added, and the mixture was stirred for 30 minutes to carry out a neutralization reaction.

The obtained suspension was equally transferred to two 50m L centrifuge tubes, and centrifuged using a high-speed cooling centrifuge (Nigri corporation, CR21G III). The supernatant was removed by decantation, and the same amount of 85% IPA aqueous solution as that of the removed supernatant was added thereto and redispersed, and the operations of centrifugation and redispersion were repeated again, and after the 3 rd centrifugation, the precipitate was taken out, and the obtained precipitate was dried under reduced pressure at 80 ℃ overnight using a vacuum dryer (Advantech, VR-420), and crushed using an Extreme mill (WARING, MX-1200XTM) to obtain a powdery cellulose derivative.

Using the obtained cellulose derivative, cleaning performance, anti-redeposition property and formulation flowability were evaluated in the same manner as in example 1

Example 14

The cellulose derivatives shown in table 1 were synthesized in the same manner as in example 13.

Further, the cleaning performance, the anti-redeposition property, and the formulation flowability were evaluated in the same manner as in example 1.

Comparative example 4

70g of HEC was put in a 1L separable flask, nitrogen gas was passed through, 56.8g of ion-exchanged water and IPA314.4g were added, and the mixture was stirred at 200r.p.m. for 5 minutes, then 8.2g of a 48% aqueous solution of sodium hydroxide was added, and further stirred for 15 minutes, then 10.4g of GMAC was added, and cationization reaction was performed at 50 ℃ for 1.5 hours, further 34.3g of 3-chloro-2-hydroxypropyldodecyldimethylammonium chloride (CDDA, manufactured by Nissan corporation) was added, and neutralization reaction was performed at 50 ℃ for 1.5 hours, and then 8.2g of a 90% aqueous solution of acetic acid was added, and the mixture was stirred for 30 minutes.

The obtained suspension was equally transferred to two 500m L centrifuge tubes, and centrifuged using a high speed cooling centrifuge (Nigri Kogyo, CR21G III), the supernatant was removed by decantation, an 85% IPA aqueous solution in an amount equal to the amount of the removed supernatant was added, and redispersed, and the operations of centrifugation and redispersion were repeated again, and after the 3 rd centrifugation, the precipitate was taken out, and the obtained precipitate was dried under reduced pressure at 80 ℃ overnight using a vacuum dryer (Advantech, VR-420), and crushed using an Extreme mill (WARING, MX-1200XTM), thereby obtaining a powdery cellulose derivative.

Using the obtained cellulose derivative, cleaning performance, anti-redeposition property and formulation flowability were evaluated in the same manner as in example 1.

[ Table 1]

The polysaccharide starting material (hydroxyalkylated polysaccharide) used in table 1 is as follows.

HEC, molecular weight 15 ten thousand: hydroxyethyl cellulose manufactured by Ashland corporation, Natrosol250JR (trade name), has a weight average molecular weight of 15 ten thousand and a degree of substitution of hydroxyethyl group of 2.5

HEC, molecular weight 9 ten thousand hydroxyethyl cellulose manufactured by Ashland corporation, Natrosol 250L R (trade name), weight average molecular weight 9 ten thousand, degree of substitution of hydroxyethyl group 2.5

HEC, molecular weight 30 ten thousand: hydroxyethyl cellulose manufactured by Ashland corporation, Natrosol250GR (trade name), has a weight average molecular weight of 30 ten thousand and a degree of substitution of hydroxyethyl group of 2.5

HEC, molecular weight 72 ten thousand: hydroxyethyl cellulose manufactured by Ashland corporation, Natrosol250MR (trade name), weight average molecular weight 72 ten thousand, and degree of substitution of hydroxyethyl group 2.5

HEC, molecular weight 100 ten thousand: hydroxyethyl cellulose manufactured by Ashland corporation, Natrosol250HR (trade name), has a weight average molecular weight of 100 ten thousand and a degree of substitution of hydroxyethyl group of 2.5

The hydrophobizing agents used in table 1 are as follows.

Glycidyl group, C12 lauryl glycidyl ether, Epogosey L A (D) (trade name) manufactured by Nissan synthetic Co., Ltd. (trade name)

Glycidyl, C16: cetyl glycidyl ether, CE-EP (trade name) manufactured by synthetic Co., Ltd., Japan

Glycidyl, C4: butyl glycidyl ether, DY-BP (trade name) manufactured by Nissan Kabushiki Kaisha

Epoxy group, C12: 1, 2-Oxetane, Wako pure chemical industries, Ltd

Glycidyl ammonium, C12: 3-chloro-2-hydroxypropyldodecyldimethylammonium chloride, CDDA (trade name) manufactured by Siri Kabushiki Kaisha

As is clear from table 1, the treatment with the polysaccharide derivative of the present invention suppresses the adhesion of sebum dirt, improves cleaning performance, and prevents the recontamination of powder dirt such as carbon black during cleaning.

Industrial applicability

According to the present invention, the cleaning performance can be improved, and the recontamination due to the powder dirt during cleaning can be suppressed. When added to detergent compositions for clothing, the polysaccharide derivatives of the present invention can impart extremely excellent effects of improving the cleaning performance and suppressing the recontamination to fabrics treated with these compositions.

Claims (19)

1. A polysaccharide derivative having a cationic group and a hydrocarbon group R having 2 or more carbon atoms,

the hydrocarbon group R is bonded directly or through a hydrocarbon group having an oxygen atom to a group obtained by removing a hydrogen atom from a hydroxyl group of a hydroxyalkylated polysaccharide,

the hydroxyalkylated polysaccharide is a hydroxyethylated polysaccharide or a hydroxypropylated polysaccharide, and has a weight average molecular weight of 1 to 74 million.

2. The polysaccharide derivative according to claim 1, wherein the degree of substitution MS of the cationic group is_CIs 0.001 to 1 inclusive.

3. The polysaccharide derivative according to claim 1 or 2, wherein the degree of substitution MS of the hydrocarbon group R_RIs 0.001 to 1 inclusive.

4. The polysaccharide derivative according to any one of claims 1 to 3, wherein the degree of substitution MS of the cationic group is_CIs 0.001-0.5 inclusive, and the degree of substitution MS of the hydrocarbon group R_RIs 0.001-0.3 inclusive.

5. The polysaccharide derivative according to any one of claims 1 to 4, wherein the degree of substitution MS of the cationic group is_CIs 0.001-0.4 inclusive, and the degree of substitution MS of the hydrocarbon group R_RIs 0.001 to 0.1 inclusive.

6. The polysaccharide derivative according to any one of claims 1 to 5, wherein the hydrocarbon group having an oxygen atom comprises an ester group and/or an ether group.

7. The polysaccharide derivative according to any one of claims 1 to 6, wherein the hydrocarbon group R is bonded to a group obtained by removing a hydrogen atom from a hydroxyl group of a hydroxyalkylated polysaccharide through a group represented by any one of the formulae (1-1-1) to (1-4):

in the formulae (1-1-1) to (1-4), R¹¹And R¹²Each independently represents an alkylene group having 2 to 4 carbon atoms, R represents a hydrocarbon group having 2 or more carbon atomsAnd a group obtained by removing a hydrogen atom from a hydroxyl group of a hydroxyalkylated polysaccharide, n1 represents-R¹¹Average molar number of addition of O-, n2 represents-R¹²The average molar number of addition of-O-, n1 and n2 being 0 to 30 inclusive.

8. The polysaccharide derivative according to any one of claims 1 to 7, wherein the number of carbons of the hydrocarbon group R is 4 or more and 22 or less.

9. The polysaccharide derivative according to any one of claims 1 to 8, wherein the number of carbons of the hydrocarbon group R is 4 or more and 16 or less.

10. The polysaccharide derivative according to any one of claims 1 to 9, wherein the polysaccharide is cellulose or guar gum.

11. The polysaccharide derivative according to any one of claims 1 to 10, wherein the cationic group is represented by formula (2-1) or formula (2-2):

in the formulae (2-1) and (2-2), R²¹～R²³Each independently represents a hydrocarbon group having 1 to 24 carbon atoms, X^-Represents an anion, n represents an integer of 0 to 3 inclusive, and represents a bonding position with a group obtained by removing a hydrogen atom from a hydroxyl group of the hydroxyalkylated polysaccharide.

12. The polysaccharide derivative according to any one of claims 1 to 11, wherein the weight average molecular weight is 1 ten thousand or more and 60 ten thousand or less.

13. The polysaccharide derivative of any one of claims 1 to 12 wherein the degree of substitution MS of the hydrocarbyl groups R is_RDegree of substitution with cationic group MS_CRatio of MS_R/MS_CIs 0.001 to 1 inclusive.

14. The polysaccharide derivative of any one of claims 1 to 13 wherein the degree of substitution MS of the hydrocarbyl groups R is_RDegree of substitution with cationic group MS_CRatio of MS_R/MS_CIs 0.005-0.8 inclusive.

15. The polysaccharide derivative of any one of claims 1 to 14, which may further have anionic groups.

16. The polysaccharide derivative according to claim 15, wherein the degree of substitution MS of the anionic group is_ADegree of substitution with cationic group MS_CRatio of MS_A/MS_CIs 3 or less.

17. The polysaccharide derivative according to claim 15 or 16, wherein the degree of substitution MS of the anionic group is_ADegree of substitution with cationic group MS_CRatio of MS_A/MS_CIs 1.5 or less.

18. The polysaccharide derivative according to any one of claims 15 to 17, wherein the degree of substitution MS of the cationic group is_CA degree of substitution MS of the hydrocarbon group of 0.001 to 0.5 inclusive_RA degree of substitution MS of the hydrocarbon group R of 0.001 to 0.3 inclusive_RDegree of substitution with cationic group MS_CRatio of MS_R/MS_C0.005-0.8, and a degree of substitution MS of anionic group_ADegree of substitution with cationic group MS_CRatio of MS_A/MS_CIs 1.5 or less.

19. A process for producing a polysaccharide derivative as claimed in any one of claims 1 to 18, wherein a hydrocarbon group R having 2 or more carbon atoms is introduced into a hydroxyalkylated polysaccharide having a weight average molecular weight of 1 to 74 ten thousand, and then the resultant is reacted with a cationizing agent.